Chemical Engineering Science最新文献_第10页

Silane-assisted regulation of bubble inhibition in polyurethane under humid conditions 硅烷在潮湿条件下对聚氨酯气泡抑制的辅助调节

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2025-12-30 DOI: 10.1016/j.ces.2025.123280

Changmei Liao , Dongzhi Wang , Jiaqi Liu , Wenqian Sang , Zhiqiang Yao , Mingdong Yu , Jianpeng Deng , Sen Yuan

Polyurethane (PU) is a polymer material widely used in coatings, composites, and elastomers owing to exceptional adhesion, high wear resistance, robust mechanical properties and tunable elasticity. However, the inherent pore defects of polyurethane limit the improvement of its mechanical properties and surface glossiness. Isocyanates are highly sensitive to moisture, leading to the formation of CO₂ bubbles. This paper for the first time proposes a one-step foaming elimination-water separation modification strategy using 3-aminopropyltriethoxysilane (APTES). APTES was used as a dual-parent defoaming reagent to prepare a series of APTES-based polyurethane resins with a good bubble-free nature, high mechanical strength, and excellent thermal stability. SEM and CT characterizations revealed that APTES served as an excellent defoaming and foam-inhibiting agent. With the addition of 3 % APTES, the porosity and average pore diameter of the polyurethane resin were eliminated, decreasing from 4.45 % and 189 μm to 0 %. This resulted in bubble-free PU5 and PU6 resins with approximately 28 % higher flexural strength and 16 % higher compressive strength than the neat resin. Additionally, the thermal stability of PU6 was effectively improved by 71.82–74.06 % in the temperature range of 400–800 °C.

聚氨酯（PU）是一种广泛应用于涂料、复合材料和弹性体的聚合物材料，具有优异的附着力、高耐磨性、坚固的机械性能和可调的弹性。然而，聚氨酯固有的孔隙缺陷限制了其机械性能和表面光泽度的提高。异氰酸酯对水分高度敏感，导致二氧化碳气泡的形成。本文首次提出了以3-氨基丙基三乙氧基硅烷（APTES）为原料的一步消泡-水分离改性策略。以APTES为双亲消泡剂，制备了一系列无泡性好、机械强度高、热稳定性好的APTES基聚氨酯树脂。SEM和CT表征表明APTES是一种优异的消泡和抑泡剂。当APTES添加量为3%时，聚氨酯树脂的孔隙率和平均孔径由4.45%和189 μm降至0%。这导致无气泡的PU5和PU6树脂比纯树脂的抗折强度高28%，抗压强度高16%。在400 ~ 800℃的温度范围内，PU6的热稳定性得到了71.82 ~ 74.06%的有效改善。

{"title":"Silane-assisted regulation of bubble inhibition in polyurethane under humid conditions","authors":"Changmei Liao , Dongzhi Wang , Jiaqi Liu , Wenqian Sang , Zhiqiang Yao , Mingdong Yu , Jianpeng Deng , Sen Yuan","doi":"10.1016/j.ces.2025.123280","DOIUrl":"10.1016/j.ces.2025.123280","url":null,"abstract":"<div><div>Polyurethane (PU) is a polymer material widely used in coatings, composites, and elastomers owing to exceptional adhesion, high wear resistance, robust mechanical properties and tunable elasticity. However, the inherent pore defects of polyurethane limit the improvement of its mechanical properties and surface glossiness. Isocyanates are highly sensitive to moisture, leading to the formation of CO<sub>2</sub> bubbles. This paper for the first time proposes a one-step foaming elimination-water separation modification strategy using 3-aminopropyltriethoxysilane (APTES). APTES was used as a dual-parent defoaming reagent to prepare a series of APTES-based polyurethane resins with a good bubble-free nature, high mechanical strength, and excellent thermal stability. SEM and CT characterizations revealed that APTES served as an excellent defoaming and foam-inhibiting agent. With the addition of 3 % APTES, the porosity and average pore diameter of the polyurethane resin were eliminated, decreasing from 4.45 % and 189 μm to 0 %. This resulted in bubble-free PU5 and PU6 resins with approximately 28 % higher flexural strength and 16 % higher compressive strength than the neat resin. Additionally, the thermal stability of PU6 was effectively improved by 71.82–74.06 % in the temperature range of 400–800 °C.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"324 ","pages":"Article 123280"},"PeriodicalIF":4.3,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145940949","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Explainable machine learning for predicting and interpreting diffusion behavior in ionic liquids 用于预测和解释离子液体扩散行为的可解释机器学习

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2025-12-30 DOI: 10.1016/j.ces.2025.123179

Ronghua Liang , Caizong Bao , Fangxin Li , Ruru Ma , Chunfa Miao , Peizhe Cui , Xin Li , Yinglong Wang , Ekemini Ituen

Ionic liquids (ILs) hold significant promise in separation, catalysis, and electrochemistry, with diffusion coefficients critically influencing their transport properties. However, accurately predicting these coefficients remains challenging. This study establishes a unified framework for predicting self-diffusion and mutual diffusion coefficients in IL systems. Three datasets were compiled, and two types of descriptors, namely molecular structural descriptors (MSD) and fragment feature descriptors (FFD), were combined with Random Forest and Multilayer Perceptron (MLP) models, whose hyperparameters were systematically optimized using Bayesian optimization. The MSD-MLP model achieved superior accuracy across all prediction tasks, with coefficients of determination ranging from 0.991 to 0.994 and the lowest error metrics, demonstrating strong generalization. Furthermore, SHapley Additive Explanations (SHAP) analysis identified the key structural features governing the diffusion performance of ionic liquids, revealed the underlying physicochemical mechanisms of diffusion, and elucidated the intrinsic structure–property relationships, providing deep insights for the rational tuning and optimization of diffusion behavior in ILs.

离子液体在分离、催化和电化学等领域具有重要的应用前景，扩散系数对离子液体的输运性质有重要影响。然而，准确预测这些系数仍然具有挑战性。本研究建立了预测IL系统自扩散和互扩散系数的统一框架。编译了3个数据集，将分子结构描述符（MSD）和片段特征描述符（FFD）两类描述符与随机森林和多层感知器（MLP）模型相结合，采用贝叶斯优化方法对其超参数进行系统优化。MSD-MLP模型在所有预测任务中均取得了较好的准确度，决定系数在0.991 ~ 0.994之间，误差指标最低，具有较强的泛化能力。此外，SHapley加性解释（SHAP）分析确定了控制离子液体扩散性能的关键结构特征，揭示了扩散的潜在物理化学机制，阐明了内在的结构-性能关系，为离子液体扩散行为的合理调整和优化提供了深刻的见解。

{"title":"Explainable machine learning for predicting and interpreting diffusion behavior in ionic liquids","authors":"Ronghua Liang , Caizong Bao , Fangxin Li , Ruru Ma , Chunfa Miao , Peizhe Cui , Xin Li , Yinglong Wang , Ekemini Ituen","doi":"10.1016/j.ces.2025.123179","DOIUrl":"10.1016/j.ces.2025.123179","url":null,"abstract":"<div><div>Ionic liquids (ILs) hold significant promise in separation, catalysis, and electrochemistry, with diffusion coefficients critically influencing their transport properties. However, accurately predicting these coefficients remains challenging. This study establishes a unified framework for predicting self-diffusion and mutual diffusion coefficients in IL systems. Three datasets were compiled, and two types of descriptors, namely molecular structural descriptors (MSD) and fragment feature descriptors (FFD), were combined with Random Forest and Multilayer Perceptron (MLP) models, whose hyperparameters were systematically optimized using Bayesian optimization. The MSD-MLP model achieved superior accuracy across all prediction tasks, with coefficients of determination ranging from 0.991 to 0.994 and the lowest error metrics, demonstrating strong generalization. Furthermore, SHapley Additive Explanations (SHAP) analysis identified the key structural features governing the diffusion performance of ionic liquids, revealed the underlying physicochemical mechanisms of diffusion, and elucidated the intrinsic structure–property relationships, providing deep insights for the rational tuning and optimization of diffusion behavior in ILs.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"323 ","pages":"Article 123179"},"PeriodicalIF":4.3,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939153","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

CFD study of enhanced stirring mechanism of swirler and lance structure in top-submerged lance bath smelting process 上浸式枪浴熔炼过程中旋流器与枪结构增强搅拌机理的CFD研究

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2025-12-29 DOI: 10.1016/j.ces.2025.123232

Zhongyu Du, Shiliang Yang, Guirong Bao, Hua Wang

The top-submerged lance (TSL) furnace is widely utilized in non-ferrous metal smelting, where the design of the lance plays a crucial role in determining smelting efficiency and process stability. This study elucidates the influence of different lance structures (i.e., varying oxygen tube diameters and mixing zone lengths) on the stirring dynamics of the TSL furnace. Based on model validation, the flow characteristics of gas within the lance are analyzed. Subsequently, the stirring zone, impact cavity, and melt splashing behavior under different lance configurations are examined. The results indicate that the addition of swirlers to the lance can convert up to 20.8 % of the axial momentum into tangential momentum, thereby ensuring tangential stirring within the bath. Reducing the diameter of the lance’s intermediate layer increases the tangential momentum at the lance outlet, resulting in a 13.4 % increase in the volume of the impact cavity. Extending the length of the mixing zone optimizes the velocity distribution and enhances the stability of gas flow, leading to a 46 % increase in the cavity volume. Utilizing the Pareto multi-objective optimization approach, optimal lance configurations for the TSL bath smelting process are delineated for two distinct production priorities: maximizing stirring efficiency and extending furnace lining longevity. The configurations, are established as D_ml = 0.149 m, L_m = 0.6 m; D_ml = 0.170 m, L_m = 0.3 m, respectively. This study provides in-depth insights into the single-phase swirling characteristics within the lance and the complex multiphase stirring behavior within the bath. The findings offer significant guidance for the optimal design of lances in practical smelting processes and provide essential theoretical support for the design, operation, and optimization of TSL furnaces.

浸没式喷枪炉在有色金属冶炼中得到广泛应用，喷枪的设计对冶炼效率和工艺稳定性起着至关重要的作用。本研究阐明了不同的喷枪结构（即不同的氧管直径和混合区长度）对TSL炉搅拌动力学的影响。在模型验证的基础上，分析了喷枪内气体的流动特性。随后，研究了不同喷枪结构下的搅拌区、冲击腔和熔体飞溅行为。结果表明，在喷管中加入旋流器可将高达20.8%的轴向动量转化为切向动量，从而保证了槽内的切向搅拌。减小喷枪中间层的直径增加了喷枪出口的切向动量，导致冲击腔的体积增加13.4%。延长混合区长度优化了速度分布，增强了气体流动的稳定性，使腔体体积增加了46%。利用Pareto多目标优化方法，对TSL熔池熔炼过程的最佳喷枪配置进行了描述，以满足两个不同的生产优先事项：最大化搅拌效率和延长炉衬寿命。构造为：Dml = 0.149 m, Lm = 0.6 m；Dml = 0.170 m, Lm = 0.3 m。该研究对喷枪内的单相旋转特性和槽内复杂的多相搅拌行为提供了深入的见解。研究结果对实际冶炼过程中钢枪的优化设计具有重要的指导意义，并为TSL炉的设计、运行和优化提供了重要的理论支持。

{"title":"CFD study of enhanced stirring mechanism of swirler and lance structure in top-submerged lance bath smelting process","authors":"Zhongyu Du, Shiliang Yang, Guirong Bao, Hua Wang","doi":"10.1016/j.ces.2025.123232","DOIUrl":"10.1016/j.ces.2025.123232","url":null,"abstract":"<div><div>The top-submerged lance (TSL) furnace is widely utilized in non-ferrous metal smelting, where the design of the lance plays a crucial role in determining smelting efficiency and process stability. This study elucidates the influence of different lance structures (i.e., varying oxygen tube diameters and mixing zone lengths) on the stirring dynamics of the TSL furnace. Based on model validation, the flow characteristics of gas within the lance are analyzed. Subsequently, the stirring zone, impact cavity, and melt splashing behavior under different lance configurations are examined. The results indicate that the addition of swirlers to the lance can convert up to 20.8 % of the axial momentum into tangential momentum, thereby ensuring tangential stirring within the bath. Reducing the diameter of the lance’s intermediate layer increases the tangential momentum at the lance outlet, resulting in a 13.4 % increase in the volume of the impact cavity. Extending the length of the mixing zone optimizes the velocity distribution and enhances the stability of gas flow, leading to a 46 % increase in the cavity volume. Utilizing the Pareto multi-objective optimization approach, optimal lance configurations for the TSL bath smelting process are delineated for two distinct production priorities: maximizing stirring efficiency and extending furnace lining longevity. The configurations, are established as <em>D<sub>ml</sub></em> = 0.149 m, <em>L<sub>m</sub></em> = 0.6 m; <em>D<sub>ml</sub></em> = 0.170 m, <em>L<sub>m</sub></em> = 0.3 m, respectively. This study provides in-depth insights into the single-phase swirling characteristics within the lance and the complex multiphase stirring behavior within the bath. The findings offer significant guidance for the optimal design of lances in practical smelting processes and provide essential theoretical support for the design, operation, and optimization of TSL furnaces.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"324 ","pages":"Article 123232"},"PeriodicalIF":4.3,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145940883","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Salinity-driven convection mechanisms in stratified brines 分层盐水中盐度驱动的对流机制

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2025-12-29 DOI: 10.1016/j.ces.2025.123224

Christian O. Oko , Berin Šeta , Aliaksandr Mialdun , Mounir M. Bou-Ali , Valentina Shevtsova , Arnault Lassin , Henri Bataller

Understanding transport and mixing in stratified saline systems is critical for predicting the behavior of brines in natural aquifers, industrial reservoirs, and engineered disposal sites. These multi-ion solutions often exhibit complex instabilities driven by differential diffusion and compositional gradients. The onset and morphology of such convective mixing remain poorly predicted. We investigated double-diffusive (DD) and diffusion-layer convection (DLC) in superimposed aqueous solutions of the salts typical of saline aquifers, sodium chloride (NaCl) and sodium sulphate (Na₂SO₄). The study combines thermodynamic modeling, optical interferometry experiments, and nonlinear numerical simulations to explore convective instabilities in a ternary system. Our findings reveal a rich variety of convective scenarios depending on salt configuration and concentration ratios. When the faster-diffusing NaCl was placed above Na₂SO₄, diffusion-layer convection occurred with a delayed and asymmetric onset of instability, an experimentally demonstrated feature not reported previously. In contrast, when the positions were reversed, the system developed double-diffusive fingers that grew slowly due to the small density ratio. These fingers exhibited an unusual morphology, consisting of extremely fine, vertically textured structures that gradually merged away from the interface. This formed a large area of diffuse mixing and suppression of coherent convective structures. In all cases, classical stability criteria failed to fully predict the onset and nature of convection. Instead, we identified the initial position of the system on the stability map, as determined by the full diffusion matrix, as a critical factor.

了解分层盐水系统中的运移和混合对于预测天然含水层、工业水库和工程处理场所中的盐水行为至关重要。这些多离子溶液通常表现出由微分扩散和成分梯度驱动的复杂不稳定性。这种对流混合的开始和形态仍然很难预测。研究了含盐含水层典型盐——氯化钠（NaCl）和硫酸钠（Na2SO4）叠加水溶液中的双扩散（DD）和扩散层对流（DLC）。该研究结合热力学模型、光学干涉实验和非线性数值模拟来探索三元体系中的对流不稳定性。我们的发现揭示了各种各样的对流情景，这取决于盐的配置和浓度比。当快速扩散的NaCl放置在Na2SO4之上时，扩散层对流发生，不稳定的延迟和不对称开始，这是以前没有报道过的实验证明的特征。相反，当位置相反时，由于密度比小，系统发展出双扩散手指，生长缓慢。这些手指表现出一种不寻常的形态，由极其精细的垂直纹理结构组成，逐渐从界面融合。这形成了大面积的漫射混合和相干对流结构的抑制。在所有的情况下，经典的稳定性判据都不能完全预测对流的开始和性质。相反，我们确定了系统在稳定性图上的初始位置，由完整的扩散矩阵确定，作为一个关键因素。

{"title":"Salinity-driven convection mechanisms in stratified brines","authors":"Christian O. Oko , Berin Šeta , Aliaksandr Mialdun , Mounir M. Bou-Ali , Valentina Shevtsova , Arnault Lassin , Henri Bataller","doi":"10.1016/j.ces.2025.123224","DOIUrl":"10.1016/j.ces.2025.123224","url":null,"abstract":"<div><div>Understanding transport and mixing in stratified saline systems is critical for predicting the behavior of brines in natural aquifers, industrial reservoirs, and engineered disposal sites. These multi-ion solutions often exhibit complex instabilities driven by differential diffusion and compositional gradients. The onset and morphology of such convective mixing remain poorly predicted. We investigated double-diffusive (DD) and diffusion-layer convection (DLC) in superimposed aqueous solutions of the salts typical of saline aquifers, sodium chloride (NaCl) and sodium sulphate (Na<sub>2</sub>SO<sub>4</sub>). The study combines thermodynamic modeling, optical interferometry experiments, and nonlinear numerical simulations to explore convective instabilities in a ternary system. Our findings reveal a rich variety of convective scenarios depending on salt configuration and concentration ratios. When the faster-diffusing NaCl was placed above Na<sub>2</sub>SO<sub>4</sub>, diffusion-layer convection occurred with a delayed and asymmetric onset of instability, an experimentally demonstrated feature not reported previously. In contrast, when the positions were reversed, the system developed double-diffusive fingers that grew slowly due to the small density ratio. These fingers exhibited an unusual morphology, consisting of extremely fine, vertically textured structures that gradually merged away from the interface. This formed a large area of diffuse mixing and suppression of coherent convective structures. In all cases, classical stability criteria failed to fully predict the onset and nature of convection. Instead, we identified the initial position of the system on the stability map, as determined by the full diffusion matrix, as a critical factor.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"324 ","pages":"Article 123224"},"PeriodicalIF":4.3,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Performance enhancement of proton exchange membrane fuel cells with conformal membrane-electrode synergistic effect 保形膜-电极协同效应增强质子交换膜燃料电池性能

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2025-12-29 DOI: 10.1016/j.ces.2025.123271

Yuzhi Ke , Wei Yuan , Shaopeng Zhang , Liang Lu , Xi Wang , Wei Zhou

Proton exchange membrane fuel cells (PEMFCs) have become a leading hydrogen energy conversion technology, where synergistic effect of the membrane-electrode component critically enhances the electrochemical performance. This work proposes a novel three-dimensional (3D) interface engineering based on the advanced surface-microstructured polymer electrolyte membrane (PEM), addressing the challenges of the high-performance output for PEMFCs under the harsh operating conditions. The optimized functional microstructures and excellent electrochemical reaction performance within the 3D PEM-catalyst layer (CL) are demonstrated without the need for external humidification and backpressure. Results show that the microstructured PEM significantly enhance the electrochemically active surface area (ECSA) and reduce the mass transport resistance within the CL. The PEMFC based on the optimized microstructured PEM (P4-membrane) exhibits excellent electrochemical performance (39.3 % enhanced peak power density and 135.8 % enhanced ECSA) and high durability (only decline rate of 0.34 mV h⁻¹ after 110 h) with the same low catalyst loading and extreme operating conditions, compared to the conventional PEMFC based on the commercial smooth PEM. We believe that the structure-controlled 3D PEM-CL architecture will provide a new pathway to design and fabricate high performance electrode for PEMFCs, as well as other electrochemical devices that require the functionalized surface and mass transfer.

质子交换膜燃料电池（PEMFCs）已成为一种领先的氢能转换技术，其膜电极组件的协同效应对提高电化学性能至关重要。这项工作提出了一种基于先进的表面微结构聚合物电解质膜（PEM）的新型三维（3D）界面工程，解决了pemfc在恶劣工作条件下高性能输出的挑战。在不需要外部加湿和背压的情况下，证明了优化后的三维pem -催化剂层（CL）的功能微结构和优异的电化学反应性能。结果表明，微结构PEM显著提高了电化学活性表面积（ECSA），降低了CL内的传质阻力。基于优化微结构PEM （p4膜）的PEMFC与基于商用光滑PEM的传统PEMFC相比，在相同的低催化剂负载和极端操作条件下，具有优异的电化学性能（峰值功率密度提高39.3%，ECSA提高135.8%）和高耐久性（110 h后仅下降0.34 mV h−1）。我们相信，结构控制的三维PEM-CL结构将为设计和制造高性能的pemfc电极以及其他需要功能化表面和传质的电化学器件提供新的途径。

{"title":"Performance enhancement of proton exchange membrane fuel cells with conformal membrane-electrode synergistic effect","authors":"Yuzhi Ke , Wei Yuan , Shaopeng Zhang , Liang Lu , Xi Wang , Wei Zhou","doi":"10.1016/j.ces.2025.123271","DOIUrl":"10.1016/j.ces.2025.123271","url":null,"abstract":"<div><div>Proton exchange membrane fuel cells (PEMFCs) have become a leading hydrogen energy conversion technology, where synergistic effect of the membrane-electrode component critically enhances the electrochemical performance. This work proposes a novel three-dimensional (3D) interface engineering based on the advanced surface-microstructured polymer electrolyte membrane (PEM), addressing the challenges of the high-performance output for PEMFCs under the harsh operating conditions. The optimized functional microstructures and excellent electrochemical reaction performance within the 3D PEM-catalyst layer (CL) are demonstrated without the need for external humidification and backpressure. Results show that the microstructured PEM significantly enhance the electrochemically active surface area (ECSA) and reduce the mass transport resistance within the CL. The PEMFC based on the optimized microstructured PEM (P4-membrane) exhibits excellent electrochemical performance (39.3 % enhanced peak power density and 135.8 % enhanced ECSA) and high durability (only decline rate of 0.34 mV h<sup>−1</sup> after 110 h) with the same low catalyst loading and extreme operating conditions, compared to the conventional PEMFC based on the commercial smooth PEM. We believe that the structure-controlled 3D PEM-CL architecture will provide a new pathway to design and fabricate high performance electrode for PEMFCs, as well as other electrochemical devices that require the functionalized surface and mass transfer.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"323 ","pages":"Article 123271"},"PeriodicalIF":4.3,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881132","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Electron structure engineering of MIL-100 via HPMo confinement for advanced oxidative desulfurization catalysis MIL-100在HPMo约束下高级氧化脱硫催化的电子结构工程

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2025-12-29 DOI: 10.1016/j.ces.2025.123275

Peiwen Wu , Kailong Yu , Shuaishuai Zhou , Jing He , Haiyan Ji , Linlin Chen , Yan Huang , Hui Liu , Jixing Liu , Huaming Li , Wenshuai Zhu

Efficient oxidative desulfurization (ODS) of aromatic sulfur compounds under mild and green conditions remains a major challenge due to the limited activation ability of molecular oxygen and poor stability of traditional catalysts. In this work, a series of HPMo@MIL-100 catalysts were synthesized for ODS of fuel oils using molecular oxygen as a green oxidant. The introduction of HPMo into the MIL-100 framework not only improved the catalytic performance but also significantly regulated the electronic environment of the Fe active centers. Structural and electronic characterizations confirmed that HPMo incorporation decreased crystallinity, increased surface defects, and facilitated electron transfer within the framework. Detailed experiments identified superoxide radicals as the dominant reactive species, efficiently generated under the synergistic effect of HPMo and MIL-100. The optimized catalyst, HPMo@MIL-100–2, achieved complete removal of aromatic sulfides within 3 h at 120 °C and the aromatic sulfides were selectively conversed to corresponding sulfones. In addition, the catalyst demonstrated excellent recyclability, which can be reused 9 times without significant decrease in ODS performance. Furthermore, a desulfurization efficiency of 95.7 % was achieved to real FCC diesel, highlighting the catalyst’s potential for industrial application. This study provides an effective strategy for tuning MOF catalytic systems through electron modulation, enabling highly efficient, selective, and recyclable ODS performance under mild conditions.

由于分子氧活化能力有限和传统催化剂稳定性差，在温和绿色条件下实现芳香族含硫化合物的高效氧化脱硫一直是一个重大挑战。本文以分子氧为绿色氧化剂，合成了一系列用于燃料油ODS的HPMo@MIL-100催化剂。在MIL-100框架中引入HPMo不仅提高了催化性能，而且显著调节了Fe活性中心的电子环境。结构和电子表征证实，HPMo掺入降低了结晶度，增加了表面缺陷，并促进了框架内的电子转移。详细实验表明，超氧自由基是主要的反应物质，在HPMo和MIL-100的协同作用下高效生成。优化后的催化剂HPMo@MIL-100 -2在120℃条件下，在3 h内实现了芳香族硫化物的完全脱除，并选择性地将芳香族硫化物转化为相应的砜。此外，该催化剂具有良好的可回收性，可重复使用9次而不显著降低ODS性能。实际催化裂化柴油的脱硫效率可达95.7%，具有较好的工业应用前景。本研究提供了通过电子调制调整MOF催化系统的有效策略，使其在温和条件下具有高效、选择性和可回收的ODS性能。

{"title":"Electron structure engineering of MIL-100 via HPMo confinement for advanced oxidative desulfurization catalysis","authors":"Peiwen Wu , Kailong Yu , Shuaishuai Zhou , Jing He , Haiyan Ji , Linlin Chen , Yan Huang , Hui Liu , Jixing Liu , Huaming Li , Wenshuai Zhu","doi":"10.1016/j.ces.2025.123275","DOIUrl":"10.1016/j.ces.2025.123275","url":null,"abstract":"<div><div>Efficient oxidative desulfurization (ODS) of aromatic sulfur compounds under mild and green conditions remains a major challenge due to the limited activation ability of molecular oxygen and poor stability of traditional catalysts. In this work, a series of HPMo@MIL-100 catalysts were synthesized for ODS of fuel oils using molecular oxygen as a green oxidant. The introduction of HPMo into the MIL-100 framework not only improved the catalytic performance but also significantly regulated the electronic environment of the Fe active centers. Structural and electronic characterizations confirmed that HPMo incorporation decreased crystallinity, increased surface defects, and facilitated electron transfer within the framework. Detailed experiments identified superoxide radicals as the dominant reactive species, efficiently generated under the synergistic effect of HPMo and MIL-100. The optimized catalyst, HPMo@MIL-100–2, achieved complete removal of aromatic sulfides within 3 h at 120 °C and the aromatic sulfides were selectively conversed to corresponding sulfones. In addition, the catalyst demonstrated excellent recyclability, which can be reused 9 times without significant decrease in ODS performance. Furthermore, a desulfurization efficiency of 95.7 % was achieved to real FCC diesel, highlighting the catalyst’s potential for industrial application. This study provides an effective strategy for tuning MOF catalytic systems through electron modulation, enabling highly efficient, selective, and recyclable ODS performance under mild conditions.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"323 ","pages":"Article 123275"},"PeriodicalIF":4.3,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Catalytic conversion of C22 alkane to aromatics over carbon (coke and activated carbon)-coated mesoporous HZSM-5: Thermodynamic and machine learning algorithm study 碳（焦炭和活性炭）包覆介孔HZSM-5催化C22烷烃转化为芳烃：热力学和机器学习算法研究

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2025-12-29 DOI: 10.1016/j.ces.2025.123274

Linyang Wang , Ming Sun , Shuo Liu , Lipeng Shao , Qiuxiang Yao

Combining the large-pore structure of carbon material with the aromatization capability of ZSM-5 offers a promising route for aromatic production. Adopting benzene as an adsorbent and coal tar asphaltene (CTA) as the carbon source, modified mesoporous ZSM-5 (YJGW/B and CTA@YJGW) were prepared ultimately. Furthermore, these catalysts were applied in the conversion of C22 alkane (C22) into aromatics using fast pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS). Ultimately, the conversion of C22 into light aromatics are analyzed by thermodynamics and machine learning. Results demonstrate that the CTA loading, as well as the carbonization and activation treatments, significantly affects the pore structure and acidity. Additionally, Py-GC/MS results illustrate that both CTA@YJGW-Car and CTA@YJGW-Act demonstrate the higher relative content of polycyclic aromatics, especially methyl-naphthalene (Nap-met) and naphthalene (N), inferring that the carbon loading promotes dehydrogenation and aromatization. YJGW-5-Act shows the highest relative content of benzene, toluene, ethylbenzene and xylene (BTEX) of 46.03 % at 500 °C. Based on the relative content changes of full compounds, the possible formation mechanism and pathways of BTEX, N and Nap-met are proposed. The thermodynamic data manifests that CTA@YJGW-Act demonstrate the greatest potential for B, T, E, X and Nap-met preparation, and machine learning exhibits that higher V_micro and lower strong acidity content are beneficial for the aromatics formation.

将碳材料的大孔结构与ZSM-5的芳构化能力相结合，为制备芳烃提供了一条很有前途的途径。以苯为吸附剂，以煤焦油沥青质（CTA）为碳源，最终制备了改性介孔ZSM-5 （YJGW/B和CTA@YJGW）。并利用快速热解-气相色谱/质谱联用技术（Py-GC/MS）将C22烷烃（C22）转化为芳烃。最后，通过热力学和机器学习分析了C22转化为轻芳烃的过程。结果表明，CTA加载、炭化和活化处理对孔隙结构和酸度有显著影响。此外，Py-GC/MS结果表明，CTA@YJGW-Car和CTA@YJGW-Act中多环芳烃的相对含量较高，尤其是甲基萘（Nap-met）和萘(N)，说明碳负载促进了脱氢和芳构化。在500℃时，YJGW-5-Act中苯、甲苯、乙苯和二甲苯（BTEX）的相对含量最高，为46.03%。根据全化合物的相对含量变化，提出了BTEX、N和Nap-met可能的形成机制和途径。热力学数据表明CTA@YJGW-Act表现出B、T、E、X和Nap-met制备的最大潜力，机器学习表明较高的Vmicro和较低的强酸性含量有利于芳烃的形成。

{"title":"Catalytic conversion of C22 alkane to aromatics over carbon (coke and activated carbon)-coated mesoporous HZSM-5: Thermodynamic and machine learning algorithm study","authors":"Linyang Wang , Ming Sun , Shuo Liu , Lipeng Shao , Qiuxiang Yao","doi":"10.1016/j.ces.2025.123274","DOIUrl":"10.1016/j.ces.2025.123274","url":null,"abstract":"<div><div>Combining the large-pore structure of carbon material with the aromatization capability of ZSM-5 offers a promising route for aromatic production. Adopting benzene as an adsorbent and coal tar asphaltene (CTA) as the carbon source, modified mesoporous ZSM-5 (YJGW/B and CTA@YJGW) were prepared ultimately. Furthermore, these catalysts were applied in the conversion of C22 alkane (C22) into aromatics using fast pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS). Ultimately, the conversion of C22 into light aromatics are analyzed by thermodynamics and machine learning. Results demonstrate that the CTA loading, as well as the carbonization and activation treatments, significantly affects the pore structure and acidity. Additionally, Py-GC/MS results illustrate that both CTA@YJGW-Car and CTA@YJGW-Act demonstrate the higher relative content of polycyclic aromatics, especially methyl-naphthalene (Nap-met) and naphthalene (N), inferring that the carbon loading promotes dehydrogenation and aromatization. YJGW-5-Act shows the highest relative content of benzene, toluene, ethylbenzene and xylene (BTEX) of 46.03 % at 500 °C. Based on the relative content changes of full compounds, the possible formation mechanism and pathways of BTEX, N and Nap-met are proposed. The thermodynamic data manifests that CTA@YJGW-Act demonstrate the greatest potential for B, T, E, X and Nap-met preparation, and machine learning exhibits that higher V<sub>micro</sub> and lower strong acidity content are beneficial for the aromatics formation.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"323 ","pages":"Article 123274"},"PeriodicalIF":4.3,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881531","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Atomic immobilization of zinc in ettringite and its thermal stability mechanisms in sewage sludge ash-cement under large temperature differences 大温差下锌在钙矾石中的原子固定化及其在污泥灰-水泥中的热稳定机理

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2025-12-29 DOI: 10.1016/j.ces.2025.123269

Jinna Shi , Jiayi Liu , Kai Lyu , Yanru Zhao , Yunhong Hao , Leonovich Sergei , Yufeng Gao

The wide application of sewage sludge ash (SSA) in producing concrete is limited by Zn leaching, especially when the concrete served under large temperature variations environments. Zn in SSA primarily exists in unstable chemical forms (exchangeable and reducible species). Under large temperature cycles, thermal stress and phase changes damage the cement microstructure and weaken heavy metal immobilization, promoting Zn release, while the key host phase ettringite (AFt) undergoes structural destabilization under such cyclic thermal loading. This study examines Zn immobilization in ettringite (AFt) under temperature cycling (−40 °C to 70 °C) using multi-scale methods. Results indicate Zn²⁺ preferentially occupies the Ca1 site in AFt (ΔE = −3.89 eV), with 10 % SSA enhancing both mechanical strength and Zn stabilization. Temperature cycling drives anisotropic Zn²⁺ migration along crystal channels, leading to dual-threshold leaching governed by high-temperature diffusion and low-temperature defect accumulation. These atomic-scale insights provide a theoretical basis for predicting long-term Zn release and ensuring the environmental safety of SSA-concrete in extreme climates.

污水污泥灰（SSA）在混凝土生产中的广泛应用受到锌浸出的限制，特别是当混凝土在温度变化较大的环境下使用时。锌在SSA中主要以不稳定的化学形式存在（交换态和还原态）。在大温度循环下，热应力和相变破坏了水泥微观结构，削弱了重金属的固定作用，促进了Zn的释放，而关键的基质相钙矾石（AFt）在这种循环热载荷下发生结构失稳。本研究使用多尺度方法在温度循环（- 40°C至70°C）下研究锌在钙矾石（AFt）中的固定化。结果表明，Zn2+优先占据AFt中的Ca1位点（ΔE =−3.89 eV）， 10%的SSA提高了机械强度和Zn稳定性。温度循环驱动Zn2+沿晶道各向异性迁移，导致高温扩散和低温缺陷积累双重阈值浸出。这些原子尺度的见解为预测锌的长期释放和确保ssa混凝土在极端气候下的环境安全提供了理论基础。

{"title":"Atomic immobilization of zinc in ettringite and its thermal stability mechanisms in sewage sludge ash-cement under large temperature differences","authors":"Jinna Shi , Jiayi Liu , Kai Lyu , Yanru Zhao , Yunhong Hao , Leonovich Sergei , Yufeng Gao","doi":"10.1016/j.ces.2025.123269","DOIUrl":"10.1016/j.ces.2025.123269","url":null,"abstract":"<div><div>The wide application of sewage sludge ash (SSA) in producing concrete is limited by Zn leaching, especially when the concrete served under large temperature variations environments. Zn in SSA primarily exists in unstable chemical forms (exchangeable and reducible species). Under large temperature cycles, thermal stress and phase changes damage the cement microstructure and weaken heavy metal immobilization, promoting Zn release, while the key host phase ettringite (AFt) undergoes structural destabilization under such cyclic thermal loading. This study examines Zn immobilization in ettringite (AFt) under temperature cycling (−40 °C to 70 °C) using multi-scale methods. Results indicate Zn<sup>2+</sup> preferentially occupies the Ca1 site in AFt (ΔE = −3.89 eV), with 10 % SSA enhancing both mechanical strength and Zn stabilization. Temperature cycling drives anisotropic Zn<sup>2+</sup> migration along crystal channels, leading to dual-threshold leaching governed by high-temperature diffusion and low-temperature defect accumulation. These atomic-scale insights provide a theoretical basis for predicting long-term Zn release and ensuring the environmental safety of SSA-concrete in extreme climates.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"323 ","pages":"Article 123269"},"PeriodicalIF":4.3,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881131","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Process intensification: Enhancing mass transfer in a gas–liquid-solid system operating an oscillatory flow reactor in continuous co-current mode 过程强化：在连续共电流模式下运行振荡流反应器的气-液-固系统中增强传质

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2025-12-29 DOI: 10.1016/j.ces.2025.123230

F. Almeida , J.A. Teixeira , F. Rocha , A. Ferreira

Process intensification (PI) demands reactor concepts that deliver high mass-transfer rates, controlled hydrodynamics and low energy consumption under continuous operation, challenges that are especially acute for three-phase (gas–liquid–solid) systems due to fouling, solids accumulation and poor gas–liquid mass transfer in conventional devices. In this research paper, the first continuous co-current study of an oscillatory flow reactor with smooth periodic constrictions (OFR-SPC) (geometry based on patent EP3057694 B1) containing suspended solids was evaluated for O₂ mass transfer, volumetric liquid-side mass transfer coefficient (

k_{L} a

), outlet O₂ concentration (

C

) and bubble dynamics at 0 and 30 % (v/v) polystyrene, while systematically varying operational conditions, oscillation amplitude (

x_{0}

) and frequency (

f

), superficial gas velocity (

u_{g}

) and liquid flow rate (

Q_{L}

). Results show that stronger oscillation and higher

u_{g}

significantly increase O₂ transfer and outlet

C

, whereas higher

Q_{L}

reduces

C

with little influence on

k_{L} a

. Under 30 % (v/v) solids the OFR-SPC exhibited fluidized bed behaviour:

C

and

k_{L} a

remained essentially invariant across the operating conditions, in contrast to semi-batch performance, in the same reactor. The reactor achieved increased mass transfer efficiency (MTE) with moderate energy demand (∼1591 W m⁻³). These findings demonstrate that continuous OFR-SPC operation can mitigate solids-related mass transfer penalties of batch systems, improving reproducibility, throughput and scale-up potential for industrial three-phase processes.

过程强化（PI）要求反应器概念在连续运行下提供高传质速率、受控流体动力学和低能耗，这对于三相（气-液-固）系统来说，由于传统设备中的污垢、固体积累和气-液传质不良，挑战尤其严重。在本研究中，首次对含悬浮固体的平滑周期缩窄（OFR-SPC）（基于专利EP3057694 B1的几何形状）振荡流动反应器进行了连续共流研究，评估了0和30% （v/v）聚苯乙烯时的O2传质、体积液侧传质系数（kLa）、出口O2浓度(C)和气泡动力学，同时系统地改变了操作条件、振荡振幅（x0）和频率(f)。表面气速（ug）和液体流速（QL）。结果表明，较强的振荡和较高的ug显著提高了O2转移量和出口C，而较高的QL降低了出口C，但对kLa影响不大。在30% （v/v）固体浓度下，OFR-SPC表现出流化床行为：C和kLa在整个操作条件下基本保持不变，与半批处理性能相反，在同一反应器中。反应器在适度的能量需求（~ 1591 W m−3）下实现了更高的传质效率（MTE）。这些发现表明，连续的OFR-SPC操作可以减轻批处理系统中固体相关的传质损失，提高工业三相工艺的再现性、吞吐量和扩大规模的潜力。

{"title":"Process intensification: Enhancing mass transfer in a gas–liquid-solid system operating an oscillatory flow reactor in continuous co-current mode","authors":"F. Almeida , J.A. Teixeira , F. Rocha , A. Ferreira","doi":"10.1016/j.ces.2025.123230","DOIUrl":"10.1016/j.ces.2025.123230","url":null,"abstract":"<div><div>Process intensification (PI) demands reactor concepts that deliver high mass-transfer rates, controlled hydrodynamics and low energy consumption under continuous operation, challenges that are especially acute for three-phase (gas–liquid–solid) systems due to fouling, solids accumulation and poor gas–liquid mass transfer in conventional devices. In this research paper, the first continuous co-current study of an oscillatory flow reactor with smooth periodic constrictions (OFR-SPC) (geometry based on patent EP3057694 B1) containing suspended solids was evaluated for O<sub>2</sub> mass transfer, volumetric liquid-side mass transfer coefficient (<span><math><mrow><msub><mi>k</mi><mi>L</mi></msub><mi>a</mi></mrow></math></span>), outlet O<sub>2</sub> concentration (<span><math><mrow><mi>C</mi></mrow></math></span>) and bubble dynamics at 0 and 30 % (v/v) polystyrene, while systematically varying operational conditions, oscillation amplitude (<span><math><mrow><msub><mi>x</mi><mn>0</mn></msub></mrow></math></span>) and frequency (<span><math><mrow><mi>f</mi></mrow></math></span>), superficial gas velocity (<span><math><mrow><msub><mi>u</mi><mi>g</mi></msub></mrow></math></span>) and liquid flow rate (<span><math><mrow><msub><mi>Q</mi><mi>L</mi></msub></mrow></math></span>). Results show that stronger oscillation and higher <span><math><mrow><msub><mi>u</mi><mi>g</mi></msub></mrow></math></span> significantly increase O<sub>2</sub> transfer and outlet <span><math><mrow><mi>C</mi></mrow></math></span>, whereas higher <span><math><mrow><msub><mi>Q</mi><mi>L</mi></msub></mrow></math></span> reduces <span><math><mrow><mi>C</mi></mrow></math></span> with little influence on <span><math><mrow><msub><mi>k</mi><mi>L</mi></msub><mi>a</mi></mrow></math></span>. Under 30 % (v/v) solids the OFR-SPC exhibited fluidized bed behaviour: <span><math><mrow><mi>C</mi></mrow></math></span> and <span><math><mrow><msub><mi>k</mi><mi>L</mi></msub><mi>a</mi></mrow></math></span> remained essentially invariant across the operating conditions, in contrast to semi-batch performance, in the same reactor. The reactor achieved increased mass transfer efficiency (<em>MTE</em>) with moderate energy demand (∼1591 W m<sup>−3</sup>). These findings demonstrate that continuous OFR-SPC operation can mitigate solids-related mass transfer penalties of batch systems, improving reproducibility, throughput and scale-up potential for industrial three-phase processes.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"323 ","pages":"Article 123230"},"PeriodicalIF":4.3,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939090","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ge optimized electron environments of binary alloy active phase loaded on nGeNi/TA catalyst to match n-ethylcarbazole orbitals to boost hydrogen storage processes Ge优化了负载在nGeNi/TA催化剂上的二元合金活性相的电子环境，以匹配n-乙基咔唑轨道，促进储氢过程

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2025-12-29 DOI: 10.1016/j.ces.2025.123273

Fei Fan , Xiaodi Zhu , Jiacan Kang , Zhenyu Song , Jianwei Liu , Hailong Wang , Anning Zhou , Houxiang Sun , Zhiping Chen , Wenwu Zhou

Developing high-performance non-precious metal catalysts for liquid organic hydrogen storage is crucial for advancing hydrogen energy technologies. Herein, we proposed a strategy in which doped Ge promoters optimized electron environments of nGeNi active phase loaded on titanium-aluminum composite oxide support with highly ordered 2D hexagonal mesopores (nGeNi/TA, n = 0, 0.5, 1, and 2 wt%), successfully establishing electron-rich active phase with high matching to HOMO orbital of N-Ethylcarbazole (NEC) molecule. Meanwhile, both d-band center of active phase and electron densities of its conduction band were effectively adjusted. These improvements not only retained ability of nGeNi active phase to activate NEC and its intermediates, but also suitably weakened strong π-d interaction with their aromatic rings. Consequently, adsorption energy of each intermediate species was almost close to average energy of hydrogenation conversion stages, thereby decreasing desorption energy of complete hydrogenation product (12H). Compared with 0GeNi/TA catalyst, NEC conversion rate on the best 1GeNi/TA catalyst at low temperature (220℃) greatly increased by approximately 118 %, and 12H selectivity and its yield sharply improved by approximately 112 % and 132 %, respectively. Moreover, excessive accumulations of intermediate species were also effectively mitigated.

开发用于液态有机储氢的高性能非贵金属催化剂是推进氢能技术发展的关键。本文提出了一种通过掺杂Ge启动子优化负载在具有高度有序二维六方介孔（nGeNi/TA, n = 0、0.5、1和2 wt%）的钛铝复合氧化物载体上的nGeNi活性相的电子环境的策略，成功建立了与n-乙基咔唑（NEC）分子HOMO轨道高度匹配的富电子活性相。同时，有效地调节了活性相d带中心和导带电子密度。这些改进不仅保留了nGeNi活性相活化NEC及其中间体的能力，而且适当地减弱了与它们的芳环强π-d相互作用。因此，各中间物质的吸附能几乎接近加氢转化阶段的平均能，从而降低了完全加氢产物的解吸能（12H）。与0GeNi/TA催化剂相比，最佳的1GeNi/TA催化剂在低温（220℃）下的NEC转化率大大提高了约118%，12H选择性和产率分别大幅提高了约112%和132%。此外，中间种的过度积累也得到了有效的缓解。

{"title":"Ge optimized electron environments of binary alloy active phase loaded on nGeNi/TA catalyst to match n-ethylcarbazole orbitals to boost hydrogen storage processes","authors":"Fei Fan , Xiaodi Zhu , Jiacan Kang , Zhenyu Song , Jianwei Liu , Hailong Wang , Anning Zhou , Houxiang Sun , Zhiping Chen , Wenwu Zhou","doi":"10.1016/j.ces.2025.123273","DOIUrl":"10.1016/j.ces.2025.123273","url":null,"abstract":"<div><div>Developing high-performance non-precious metal catalysts for liquid organic hydrogen storage is crucial for advancing hydrogen energy technologies. Herein, we proposed a strategy in which doped Ge promoters optimized electron environments of nGeNi active phase loaded on titanium-aluminum composite oxide support with highly ordered 2D hexagonal mesopores (nGeNi/TA, n = 0, 0.5, 1, and 2 wt%), successfully establishing electron-rich active phase with high matching to HOMO orbital of N-Ethylcarbazole (NEC) molecule. Meanwhile, both d-band center of active phase and electron densities of its conduction band were effectively adjusted. These improvements not only retained ability of nGeNi active phase to activate NEC and its intermediates, but also suitably weakened strong π-d interaction with their aromatic rings. Consequently, adsorption energy of each intermediate species was almost close to average energy of hydrogenation conversion stages, thereby decreasing desorption energy of complete hydrogenation product (12H). Compared with 0GeNi/TA catalyst, NEC conversion rate on the best 1GeNi/TA catalyst at low temperature (220℃) greatly increased by approximately 118 %, and 12H selectivity and its yield sharply improved by approximately 112 % and 132 %, respectively. Moreover, excessive accumulations of intermediate species were also effectively mitigated.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"323 ","pages":"Article 123273"},"PeriodicalIF":4.3,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881205","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0