Pub Date : 2026-03-24DOI: 10.1021/acs.iecr.6c00048
Guoquan Wu,Keerthana Vellayappan,Yao Shi,Zhe Wu
Physics-informed neural networks (PINNs) embed physical constraints into neural network training and are effective for modeling chemical processes. However, standard PINNs with uniformly sampled collocation points and manually tuned or fixed loss weights often suffer from poor training efficiency and accuracy, as adjusting loss weights is challenging and problem-dependent. To address these issues, this work proposes a Pareto-guided regional sampling (PaRS) framework for adaptive collocation point sampling and loss balancing. PaRS integrates residual decomposition, adaptive loss weighting, and dynamic resampling. The spatial domain is partitioned into subregions, and residuals from different regions are treated as competing objectives, forming a Pareto front that captures trade-offs among losses. A Pareto-guided weighting strategy then assigns adaptive weights based on training progress, which further guides region-wise resampling to focus on error-prone or underexplored areas. Case studies in chemical engineering demonstrate that PaRS-PINNs outperform standard PINNs and existing adaptive collocation methods.
{"title":"Adaptive Weighting and Collocation in Physics-Informed Neural Networks for Chemical Process Modeling","authors":"Guoquan Wu,Keerthana Vellayappan,Yao Shi,Zhe Wu","doi":"10.1021/acs.iecr.6c00048","DOIUrl":"https://doi.org/10.1021/acs.iecr.6c00048","url":null,"abstract":"Physics-informed neural networks (PINNs) embed physical constraints into neural network training and are effective for modeling chemical processes. However, standard PINNs with uniformly sampled collocation points and manually tuned or fixed loss weights often suffer from poor training efficiency and accuracy, as adjusting loss weights is challenging and problem-dependent. To address these issues, this work proposes a Pareto-guided regional sampling (PaRS) framework for adaptive collocation point sampling and loss balancing. PaRS integrates residual decomposition, adaptive loss weighting, and dynamic resampling. The spatial domain is partitioned into subregions, and residuals from different regions are treated as competing objectives, forming a Pareto front that captures trade-offs among losses. A Pareto-guided weighting strategy then assigns adaptive weights based on training progress, which further guides region-wise resampling to focus on error-prone or underexplored areas. Case studies in chemical engineering demonstrate that PaRS-PINNs outperform standard PINNs and existing adaptive collocation methods.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"16 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506370","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-24DOI: 10.1021/acs.iecr.6c00181
Andre Luis Carvalho Souza,Raul José Alves Felisardo,Robson da Silva Souto,Renata Colombo,Marcos Roberto de Vasconcelos Lanza
This study reports the optimization of a continuous-flow electrochemical reactor with concentric cube geometry designed for the in-situ production of hydrogen peroxide (H2O2). The system, developed using a Printex L6 carbon-based gas diffusion electrode (GDE), was optimized and applied for high-efficiency H2O2 generation and the remediation of atrazine (ATZ) contaminated water. The initial analysis of different volumetric flow rates (200, 400, and 800 mL min–1) showed that the rate of 400 mL min–1 offered the best balance between H2O2 production efficiency, energy consumption (7.57 kWh kg–1), and current efficiency (78.1%). A central composite rotatable design (CCRD) was applied for the analysis of the effects of current density, electrolyte concentration, oxygen flow rate, and pH. The CCRD model exhibited high predictive accuracy (R2 > 0.96), with current density and pH identified as the most influential factors. With a working volume of 1 L, under optimal conditions (0.075 mol L–1 K2SO4, 20 mA cm–2, 0.05 L min–1 O2, pH 5), 848 mg L–1 of H2O2 were generated in 30 min. Among the oxidative processes tested, the combined AO/e-H2O2/UVC treatment recorded >90% ATZ removal and >23% mineralization in 30 min, evidencing a strong synergistic effect attributed to UVC-induced H2O2 photolysis and hydroxyl radical formation. LC-MS/MS analysis confirmed the formation of 11 oxidative intermediates, where the degradation pathways were found to involve dechlorination, N-dealkylation, and cleavage of the s-triazine ring. The results of this study highlight the application potential of innovative reactor designs for efficient H2O2 electrogeneration and sustainable mitigation of persistent organic pollutants.
本研究报道了一个同心立方结构的连续流电化学反应器的优化设计，用于原位生产过氧化氢（H2O2）。该系统采用Printex L6碳基气体扩散电极（GDE）开发，经优化并应用于高效生成H2O2和修复阿特拉津（ATZ）污染的水。对不同体积流量（200、400和800 mL min-1）的初步分析表明，400 mL min-1流速在H2O2生产效率、能耗（7.57 kWh kg-1）和当前效率（78.1%）之间取得了最佳平衡。采用中心复合旋转设计（CCRD）分析电流密度、电解质浓度、氧流速和pH的影响。CCRD模型具有较高的预测精度（R2 > 0.96），其中电流密度和pH是影响最大的因素。在工作体积为1 L的条件下（0.075 mol L - 1 K2SO4, 20 mA cm-2, 0.05 L min - 1 O2, pH 5）， 30 min可生成848 mg L - 1 H2O2。在测试的氧化过程中，AO/e-H2O2/UVC联合处理在30分钟内记录了>90%的ATZ去除和>23%的矿化，这表明UVC诱导的H2O2光解和羟基自由基形成具有很强的协同效应。LC-MS/MS分析证实了11个氧化中间体的形成，其中降解途径涉及脱氯、n -脱烷基和s-三嗪环的裂解。该研究结果强调了创新反应器设计在高效H2O2发电和可持续缓解持久性有机污染物方面的应用潜力。
{"title":"Using an Innovative Concentric Cube Electrochemical Reactor for High-Efficiency H2O2 Production and Atrazine Degradation","authors":"Andre Luis Carvalho Souza,Raul José Alves Felisardo,Robson da Silva Souto,Renata Colombo,Marcos Roberto de Vasconcelos Lanza","doi":"10.1021/acs.iecr.6c00181","DOIUrl":"https://doi.org/10.1021/acs.iecr.6c00181","url":null,"abstract":"This study reports the optimization of a continuous-flow electrochemical reactor with concentric cube geometry designed for the in-situ production of hydrogen peroxide (H2O2). The system, developed using a Printex L6 carbon-based gas diffusion electrode (GDE), was optimized and applied for high-efficiency H2O2 generation and the remediation of atrazine (ATZ) contaminated water. The initial analysis of different volumetric flow rates (200, 400, and 800 mL min–1) showed that the rate of 400 mL min–1 offered the best balance between H2O2 production efficiency, energy consumption (7.57 kWh kg–1), and current efficiency (78.1%). A central composite rotatable design (CCRD) was applied for the analysis of the effects of current density, electrolyte concentration, oxygen flow rate, and pH. The CCRD model exhibited high predictive accuracy (R2 > 0.96), with current density and pH identified as the most influential factors. With a working volume of 1 L, under optimal conditions (0.075 mol L–1 K2SO4, 20 mA cm–2, 0.05 L min–1 O2, pH 5), 848 mg L–1 of H2O2 were generated in 30 min. Among the oxidative processes tested, the combined AO/e-H2O2/UVC treatment recorded >90% ATZ removal and >23% mineralization in 30 min, evidencing a strong synergistic effect attributed to UVC-induced H2O2 photolysis and hydroxyl radical formation. LC-MS/MS analysis confirmed the formation of 11 oxidative intermediates, where the degradation pathways were found to involve dechlorination, N-dealkylation, and cleavage of the s-triazine ring. The results of this study highlight the application potential of innovative reactor designs for efficient H2O2 electrogeneration and sustainable mitigation of persistent organic pollutants.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"16 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506373","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-24DOI: 10.1021/acs.iecr.5c04964
Ivan V. Shamsutov,Alexey A. Markov,Oleg V. Merkulov
A comparative thermodynamic analysis of the three-stage CLRWS process (methane reforming, water splitting, and air reoxidation) was performed for iron-based oxygen carriers, including Fe2O3 supported on SiO2, TiO2, MgO, MgAl2O4, and YSZ, alongside the self-supported SrFe12O19. While CH4 conversion and syngas yield were similar, carbon deposition varied significantly, being lowest for SrFe12O19 and Fe2O3/MgAl2O4. Stable phase formation (Fe2SiO4, FeTiO3) on SiO2 and TiO2 limited reduction depth and oxygen availability. SrFe12O19 exhibited the highest metallic iron content, enabling a hydrogen yield of 10.6 mmol/g at >98% purity. Carriers with inert supports (YSZ, MgAl2O4) exhibited classical oxidation, while others formed mixed oxides that could hinder regeneration. All systems required external heat, with the highest demand for YSZ-, MgAl2O4-, and SrFe12O19-based carriers. Steam input variation enabled hydrogen output control and potential autothermal operation. Overall, Fe2O3/MgAl2O4 and SrFe12O19 showed the best potential for CLRWS, combining low carbon deposition, high reversibility, and thermal flexibility.
{"title":"Thermodynamic Screening of SrFe12O19 vs Supported Fe2O3 Oxygen Carriers for Chemical Looping Reforming with Water Splitting","authors":"Ivan V. Shamsutov,Alexey A. Markov,Oleg V. Merkulov","doi":"10.1021/acs.iecr.5c04964","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04964","url":null,"abstract":"A comparative thermodynamic analysis of the three-stage CLRWS process (methane reforming, water splitting, and air reoxidation) was performed for iron-based oxygen carriers, including Fe2O3 supported on SiO2, TiO2, MgO, MgAl2O4, and YSZ, alongside the self-supported SrFe12O19. While CH4 conversion and syngas yield were similar, carbon deposition varied significantly, being lowest for SrFe12O19 and Fe2O3/MgAl2O4. Stable phase formation (Fe2SiO4, FeTiO3) on SiO2 and TiO2 limited reduction depth and oxygen availability. SrFe12O19 exhibited the highest metallic iron content, enabling a hydrogen yield of 10.6 mmol/g at >98% purity. Carriers with inert supports (YSZ, MgAl2O4) exhibited classical oxidation, while others formed mixed oxides that could hinder regeneration. All systems required external heat, with the highest demand for YSZ-, MgAl2O4-, and SrFe12O19-based carriers. Steam input variation enabled hydrogen output control and potential autothermal operation. Overall, Fe2O3/MgAl2O4 and SrFe12O19 showed the best potential for CLRWS, combining low carbon deposition, high reversibility, and thermal flexibility.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"20 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506378","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-23DOI: 10.1021/acs.iecr.5c04900
Luca Mastroianni, Giuseppe Agovino, Kari Eränen, Martino Di Serio, Vincenzo Russo, Dmitry Yu Murzin, Tapio Salmi
3D printing, or additive manufacturing, is transforming the whole concept of manufacturing. When applied to catalyst shaping, 3D printing enables the creation of new architectures with the potential to significantly improve the mass and heat transfer rates in continuous reactors. This work analyzed the manufacturing process of structured γ-Al2O3 catalyst elements with the digital light processing (DLP) 3D printing technology. The influence of printing parameters and resin composition on the printability of ceramic resins was rationalized by developing a qualitative force balance for DLP printing, providing a framework to guide the formulation of ceramic resins for the production of heterogeneous catalysts. Dimensional accuracy studies were carried out to reveal the effect of light scattering on the resolution of the printed bodies along different directions. The strength of the structured bodies after polymer thermolysis was enhanced through repeated infiltration with colloidal boehmite nanoparticles with intermediate thermal treatments. The surface area was kept in a catalytically relevant range by using this approach. The effect of the printed lattice and wall thickness on the final mechanical performance was investigated, revealing the main parameters influencing the strength of the printed bodies. Drop tests demonstrated the robustness of the printed catalysts under impact. Overall, this study provides new insights into the design, fabrication, and strength of DLP 3D-printed structured catalysts, establishing a foundation for their future implementation in intensified catalytic reactors.
{"title":"Digital Light Processing 3D Printing of Structured γ-Al2O3 Catalysts: Manufacturing Challenges and Mechanical Performance","authors":"Luca Mastroianni, Giuseppe Agovino, Kari Eränen, Martino Di Serio, Vincenzo Russo, Dmitry Yu Murzin, Tapio Salmi","doi":"10.1021/acs.iecr.5c04900","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04900","url":null,"abstract":"3D printing, or additive manufacturing, is transforming the whole concept of manufacturing. When applied to catalyst shaping, 3D printing enables the creation of new architectures with the potential to significantly improve the mass and heat transfer rates in continuous reactors. This work analyzed the manufacturing process of structured γ-Al<sub>2</sub>O<sub>3</sub> catalyst elements with the digital light processing (DLP) 3D printing technology. The influence of printing parameters and resin composition on the printability of ceramic resins was rationalized by developing a qualitative force balance for DLP printing, providing a framework to guide the formulation of ceramic resins for the production of heterogeneous catalysts. Dimensional accuracy studies were carried out to reveal the effect of light scattering on the resolution of the printed bodies along different directions. The strength of the structured bodies after polymer thermolysis was enhanced through repeated infiltration with colloidal boehmite nanoparticles with intermediate thermal treatments. The surface area was kept in a catalytically relevant range by using this approach. The effect of the printed lattice and wall thickness on the final mechanical performance was investigated, revealing the main parameters influencing the strength of the printed bodies. Drop tests demonstrated the robustness of the printed catalysts under impact. Overall, this study provides new insights into the design, fabrication, and strength of DLP 3D-printed structured catalysts, establishing a foundation for their future implementation in intensified catalytic reactors.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"1 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496389","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dry reforming of methane (DRM) offers a promising strategy that concomitantly converts two greenhouse gases (CH4 and CO2) into valuable syngas (H2 and CO). Ni is a commonly used active metal component in DRM catalysts, while catalyst deactivation stemming from carbon accumulation and sintering remains a great challenge. Ensuring the availability of adequate active oxygen species to promote CHx (x = 0∼3) oxidation and inhibit particle aggregation is generally critical to prevent catalyst deactivation. Our study applied a simple coprecipitation method to synthesize Ni/CexMgO catalysts for the DRM reaction, while the calcination temperatures have been first found to play an important role in controlling their catalytic performance. Interestingly, with higher temperature treatment, the Ni/Ce0.005MgO-800 catalyst with a certain amount of Ce doping exhibited the greatest activity (conversion of 73.5% for CH4 and 82.3% for CO2 at 750 °C under a weight hourly space velocity of 30,000 mL·gcat–1·h–1). Moreover, the catalytic activity can remain stable within 40 h running at 750 °C, and no carbon accumulation was detected on the used catalyst. A series of characterization results showed that both increasing the calcination temperature and Ce doping can increase the weakly basic sites and oxygen vacancy of the catalyst, thereby intensifying the adsorption and activation capabilities for CO2 and generating more reactive oxygen species, accelerating the removal of unexpected deposited carbon. Meanwhile, the higher calcination temperature might promote electron transfer between Ni, Mg, and Ce, consequently strengthening the metal–support interaction and inhibiting the sintering of Ni.
{"title":"High-Temperature Calcination Improves Catalytic Activity and Stability of Ce-Doped Ni/MgO Nanocatalysts for Dry Reforming of Methane","authors":"Jinjin Liu, Qijie Yi, Jiajian Gao, Chi Zhang, Zongpeng Zou, Shengwei Tang, Wenxiang Tang","doi":"10.1021/acs.iecr.6c00367","DOIUrl":"https://doi.org/10.1021/acs.iecr.6c00367","url":null,"abstract":"Dry reforming of methane (DRM) offers a promising strategy that concomitantly converts two greenhouse gases (CH<sub>4</sub> and CO<sub>2</sub>) into valuable syngas (H<sub>2</sub> and CO). Ni is a commonly used active metal component in DRM catalysts, while catalyst deactivation stemming from carbon accumulation and sintering remains a great challenge. Ensuring the availability of adequate active oxygen species to promote CH<sub><i>x</i></sub> (<i>x</i> = 0∼3) oxidation and inhibit particle aggregation is generally critical to prevent catalyst deactivation. Our study applied a simple coprecipitation method to synthesize Ni/Ce<sub><i>x</i></sub>MgO catalysts for the DRM reaction, while the calcination temperatures have been first found to play an important role in controlling their catalytic performance. Interestingly, with higher temperature treatment, the Ni/Ce<sub>0.005</sub>MgO-800 catalyst with a certain amount of Ce doping exhibited the greatest activity (conversion of 73.5% for CH<sub>4</sub> and 82.3% for CO<sub>2</sub> at 750 °C under a weight hourly space velocity of 30,000 mL·g<sub>cat</sub><sup>–1</sup>·h<sup>–1</sup>). Moreover, the catalytic activity can remain stable within 40 h running at 750 °C, and no carbon accumulation was detected on the used catalyst. A series of characterization results showed that both increasing the calcination temperature and Ce doping can increase the weakly basic sites and oxygen vacancy of the catalyst, thereby intensifying the adsorption and activation capabilities for CO<sub>2</sub> and generating more reactive oxygen species, accelerating the removal of unexpected deposited carbon. Meanwhile, the higher calcination temperature might promote electron transfer between Ni, Mg, and Ce, consequently strengthening the metal–support interaction and inhibiting the sintering of Ni.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"86 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507248","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The construction of advanced catalysts with well-defined structural properties is crucial for the selective hydrogenation of polyaromatic hydrocarbons in modern fossil fuel upgrading. In this work, a PtPd alloy catalyst supported on Si-modified Al2O3 nanosheet (Pt-Pd/A-Si-12) is synthesized, which exhibits three key structural advantages: a high specific surface area (422 m2 g–1), a large pore volume (0.8 cm3 g–1), and a surface enriched with finely modulated weak acid sites. Systematic characterization reveals that the hierarchical porous structure not only promotes uniform dispersion of active metal species but also facilitates mass transfer of macromolecular reactants, leading to a diffusion rate 1.47 times that of the unmodified Pt-Pd/A-Si-0 catalyst. Moreover, the tailored weak acid sites play a dual role: enhancing the metal–support interaction through electronic effects while concurrently creating a highly selective hydrogenation environment. As a result, the Pt-Pd/A-Si-12 catalyst achieves nearly complete conversion (∼100%) and a selectivity up to 93% under 250 °C and 5 MPa H2, along with significantly improved stability and high sulfur resistance. This study provides fundamental insights into the structure–performance relationship in selective hydrogenation and offers an effective strategy for the design of efficient industrial catalysts.
构建结构性能明确的先进催化剂是现代化石燃料升级过程中多芳烃选择性加氢反应的关键。在这项工作中，合成了一种负载在si修饰Al2O3纳米片上的PtPd合金催化剂（Pt-Pd/ a - si -12），它具有三个关键的结构优势：高比表面积（422 m2 g-1），大孔体积（0.8 cm3 g-1），表面富含精细调制的弱酸位点。系统表征表明，分级多孔结构不仅促进了活性金属的均匀分散，而且有利于大分子反应物的传质，其扩散速率是未改性Pt-Pd/ a - si -0催化剂的1.47倍。此外，定制的弱酸位点具有双重作用：通过电子效应增强金属-载体相互作用，同时创造高选择性的氢化环境。结果表明，Pt-Pd/ a - si -12催化剂在250°C和5 MPa H2条件下实现了几乎完全的转化（~ 100%）和高达93%的选择性，同时显著提高了稳定性和高抗硫性。本研究为研究选择性加氢反应的结构-性能关系提供了基础，并为高效工业催化剂的设计提供了有效的策略。
{"title":"Superior Catalytic Performance of Si-Modified Al2O3 Nanosheets Supported PtPd Alloy in Selective Hydrogenation of Naphthalene","authors":"Yanfu Tong, Weilong Xie, Huixian Sun, Jiachang Xu, Chenghua Yin, Xuejiao Chen, Hao Wu, Zhenxiang Zhao, Pingping Wu, Chunzheng Wang, Peng Bai, Wei Xing, Zifeng Yan","doi":"10.1021/acs.iecr.5c05223","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c05223","url":null,"abstract":"The construction of advanced catalysts with well-defined structural properties is crucial for the selective hydrogenation of polyaromatic hydrocarbons in modern fossil fuel upgrading. In this work, a PtPd alloy catalyst supported on Si-modified Al<sub>2</sub>O<sub>3</sub> nanosheet (Pt-Pd/A-Si-12) is synthesized, which exhibits three key structural advantages: a high specific surface area (422 m<sup>2</sup> g<sup>–1</sup>), a large pore volume (0.8 cm<sup>3</sup> g<sup>–1</sup>), and a surface enriched with finely modulated weak acid sites. Systematic characterization reveals that the hierarchical porous structure not only promotes uniform dispersion of active metal species but also facilitates mass transfer of macromolecular reactants, leading to a diffusion rate 1.47 times that of the unmodified Pt-Pd/A-Si-0 catalyst. Moreover, the tailored weak acid sites play a dual role: enhancing the metal–support interaction through electronic effects while concurrently creating a highly selective hydrogenation environment. As a result, the Pt-Pd/A-Si-12 catalyst achieves nearly complete conversion (∼100%) and a selectivity up to 93% under 250 °C and 5 MPa H<sub>2</sub>, along with significantly improved stability and high sulfur resistance. This study provides fundamental insights into the structure–performance relationship in selective hydrogenation and offers an effective strategy for the design of efficient industrial catalysts.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"19 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496390","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-23DOI: 10.1021/acs.iecr.5c05048
Ruifeng Luo, Bo Chen, Lin Liu, Changyi Chen, Haodong Huang, Caiwei Wang, Yuanyuan Ge, Zhili Li
Designing catalysts with precisely balanced acid-metal bifunctional sites is a central challenge in the selective conversion of biomass. In this work, we report a bifunctional Ru1.5/Fe36–SiO2 catalyst developed through a simple and scalable two-step synthesis involving coprecipitation and impregnation. This catalyst demonstrated exceptional performance in the selective C–C and C–O bond cleavage of sucrose, with near-complete conversion (>99%) and a high total carbon yield of 82.2% to diols and lower alcohols. Notably, the carbon yield of the main product, 1,2-propanediol, reached 52.5%, surpassing the performance of most previously reported Ru-based catalysts. Characterization revealed that the catalyst with an optimal Fe content of 36 wt % possessed a high specific surface area (249.66 m2/g). This composition created an acidic environment enriched with weak to medium-strength acids, predominantly of the Lewis type. More importantly, it induced the formation of abundant Ru–Fe2O3 interfaces. At this interface, charge transfer generates Ru0 sites with optimal electron density, which synergize with the predominantly Lewis acid sites of weak to moderate strength. This synergy not only promotes retro-aldol condensation and selective hydrogenolysis but also suppresses side reactions like deep dehydration and excessive C–C bond cleavage. The catalyst exhibited excellent stability, retaining over 94% of its initial activity after four consecutive cycles. Furthermore, its activity could be fully restored through a simple reduction treatment, highlighting its strong potential for industrial applications. This work offers a valuable strategy for tuning metal-acid synergy to design highly efficient supported catalysts for complex reaction networks.
{"title":"Synergistic Catalysis at Engineered Ru–Fe2O3 Interfaces on Iron Silicate for Selective Conversion of Sucrose to Diols and Lower Alcohols","authors":"Ruifeng Luo, Bo Chen, Lin Liu, Changyi Chen, Haodong Huang, Caiwei Wang, Yuanyuan Ge, Zhili Li","doi":"10.1021/acs.iecr.5c05048","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c05048","url":null,"abstract":"Designing catalysts with precisely balanced acid-metal bifunctional sites is a central challenge in the selective conversion of biomass. In this work, we report a bifunctional Ru<sub>1.5</sub>/Fe<sub>36</sub>–SiO<sub>2</sub> catalyst developed through a simple and scalable two-step synthesis involving coprecipitation and impregnation. This catalyst demonstrated exceptional performance in the selective C–C and C–O bond cleavage of sucrose, with near-complete conversion (>99%) and a high total carbon yield of 82.2% to diols and lower alcohols. Notably, the carbon yield of the main product, 1,2-propanediol, reached 52.5%, surpassing the performance of most previously reported Ru-based catalysts. Characterization revealed that the catalyst with an optimal Fe content of 36 wt % possessed a high specific surface area (249.66 m<sup>2</sup>/g). This composition created an acidic environment enriched with weak to medium-strength acids, predominantly of the Lewis type. More importantly, it induced the formation of abundant Ru–Fe<sub>2</sub>O<sub>3</sub> interfaces. At this interface, charge transfer generates Ru<sup>0</sup> sites with optimal electron density, which synergize with the predominantly Lewis acid sites of weak to moderate strength. This synergy not only promotes retro-aldol condensation and selective hydrogenolysis but also suppresses side reactions like deep dehydration and excessive C–C bond cleavage. The catalyst exhibited excellent stability, retaining over 94% of its initial activity after four consecutive cycles. Furthermore, its activity could be fully restored through a simple reduction treatment, highlighting its strong potential for industrial applications. This work offers a valuable strategy for tuning metal-acid synergy to design highly efficient supported catalysts for complex reaction networks.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"37 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496644","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This paper reports the synthesis of a novel organosilicon cationic Gemini surfactant (GSC-12C) and the surface properties of GSC-12C/cocamidopropyl betaine (CAB) aqueous solution. GSC-12C exhibited high surface activity in aqueous solution, with the critical micelle concentration (CMC) of 0.20 mmol/L, and the corresponding surface tension (γCMC) was 20.7 mN/m, which is superior to that of the perfluorooctanesulfonate (C7F15COONa, CMC = 31.2 mmol/L,γCMC = 24.7 mN/m). It had the ability to comprehensively replace perfluorinated surfactants. Moreover, when the gemini cationic organosilicon surfactant (GSC-12C) was compounded with common hydrocarbon surfactants, it was found that it had a good synergistic effect with CAB and could enhance the foaming and foam-stabilizing abilities of the surfactant. Additionally, the GSC-12C solution exhibited excellent wettability, enabling the PTFE membrane to be nearly completely wetted at a very low concentration (1 mmol/L). This work broadens the ideas for the preparation and formulation of high-performance specialty surfactants.
{"title":"Surface Activity, Aggregation Behavior, Wettability, and Foam Properties of Mixed System of Gemini Cationic Silicon Surfactant and Betaine Hydrocarbon Surfactant in Dilute Solutions","authors":"Ding Zhang, Yihan Xiong, Mengyuan Peng, Shijuan Ying, Biao Jiang","doi":"10.1021/acs.iecr.6c00018","DOIUrl":"https://doi.org/10.1021/acs.iecr.6c00018","url":null,"abstract":"This paper reports the synthesis of a novel organosilicon cationic Gemini surfactant (GSC-12C) and the surface properties of GSC-12C/cocamidopropyl betaine (CAB) aqueous solution. GSC-12C exhibited high surface activity in aqueous solution, with the critical micelle concentration (CMC) of 0.20 mmol/L, and the corresponding surface tension (γ<sub>CMC</sub>) was 20.7 mN/m, which is superior to that of the perfluorooctanesulfonate (C<sub>7</sub>F<sub>15</sub>COONa, CMC = 31.2 mmol/L,γ<sub>CMC</sub> = 24.7 mN/m). It had the ability to comprehensively replace perfluorinated surfactants. Moreover, when the gemini cationic organosilicon surfactant (GSC-12C) was compounded with common hydrocarbon surfactants, it was found that it had a good synergistic effect with CAB and could enhance the foaming and foam-stabilizing abilities of the surfactant. Additionally, the GSC-12C solution exhibited excellent wettability, enabling the PTFE membrane to be nearly completely wetted at a very low concentration (1 mmol/L). This work broadens the ideas for the preparation and formulation of high-performance specialty surfactants.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"17 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496430","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chemical demulsifiers represent an effective strategy for breaking water-in-crude-oil (W/O) emulsions. In this study, we report the synthesis and application of innovative, ecologically friendly, and effective demulsifiers based on microcrystalline cellulose (CEL) functionalized with imidazolium-based poly(ionic liquid)s for breaking the W/O emulsions at ambient temperature. Two ionic liquid (IL) monomers ([VIm-Trz-C6][Br] and [VIm-Trz-C6][BF4]) were synthesized and grafted onto the CEL@SiPBr macroinitiator using the surface-initiated atom transfer radical polymerization (SI-ATRP) technique. The degree of crystallinity dropped from 70% for CEL to 41% for CEL@P[VIm-Trz-C6][BF4]. In the range of 1000–4000 ppm, the synthesized compound was utilized as a demulsifier for the demulsification of 10:90 and 30:70 v/v% W/O emulsions. The CEL@P[VIm-Trz-C6][BF4] at 3000 ppm showed the maximum dehydration efficiency (DE), according to the bottle test results. A significant reduction in interfacial tension (IFT) was achieved using the demulsifier CEL@P[VIm-Trz-C6][BF4]. These new demulsifiers, based on microcrystalline CEL modified with imidazolium-based poly(ionic liquid)s, demonstrated high effectiveness in breaking water-in-oil emulsions while offering economic and environmental advantages. The use of CEL as a sustainable base material combined with a low ratio of ionic liquid ensures cost-efficiency and minimizes ecological impact, positioning these materials as promising candidates for crude oil emulsion treatment.
{"title":"Cellulose Modified with Poly(ionic liquid)s via SI-ATRP as an Efficient Demulsifier for Breaking Water-in-Crude-Oil Emulsions at Room Temperature","authors":"Roya Nouri, Zeinab Zargari, Hamed Sadighian, Ebrahim Ahmadi, Zahra Mohamadnia, Abolfazl Heydari","doi":"10.1021/acs.iecr.5c05261","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c05261","url":null,"abstract":"Chemical demulsifiers represent an effective strategy for breaking water-in-crude-oil (W/O) emulsions. In this study, we report the synthesis and application of innovative, ecologically friendly, and effective demulsifiers based on microcrystalline cellulose (CEL) functionalized with imidazolium-based poly(ionic liquid)s for breaking the W/O emulsions at ambient temperature. Two ionic liquid (IL) monomers ([VIm-Trz-C6][Br] and [VIm-Trz-C6][BF<sub>4</sub>]) were synthesized and grafted onto the CEL@SiPBr macroinitiator using the surface-initiated atom transfer radical polymerization (SI-ATRP) technique. The degree of crystallinity dropped from 70% for CEL to 41% for CEL@P[VIm-Trz-C6][BF<sub>4</sub>]. In the range of 1000–4000 ppm, the synthesized compound was utilized as a demulsifier for the demulsification of 10:90 and 30:70 v/v% W/O emulsions. The CEL@P[VIm-Trz-C6][BF<sub>4</sub>] at 3000 ppm showed the maximum dehydration efficiency (DE), according to the bottle test results. A significant reduction in interfacial tension (IFT) was achieved using the demulsifier CEL@P[VIm-Trz-C6][BF<sub>4</sub>]. These new demulsifiers, based on microcrystalline CEL modified with imidazolium-based poly(ionic liquid)s, demonstrated high effectiveness in breaking water-in-oil emulsions while offering economic and environmental advantages. The use of CEL as a sustainable base material combined with a low ratio of ionic liquid ensures cost-efficiency and minimizes ecological impact, positioning these materials as promising candidates for crude oil emulsion treatment.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"1 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490118","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The separation of the iso-propanol (IPA)-water azeotrope is a significant challenge in the chemical and biomedical industries, primarily due to strong hydrogen bonding interactions that hinder conventional distillation. Although extractive distillation offers a viable solution, conventional entrainers suffer from limitations such as corrosion, volatility, and environmental issues. Ionic liquids (ILs) have emerged as promising green alternatives owing to their negligible vapor pressure, high thermal stability, and tunable properties. In this study, three acetate-based ammonium ILs─[N1111][Ac], [N2111][Ac], and [N4111][Ac]─were systematically screened using the COSMO-RS model. Isobaric vapor–liquid equilibrium (VLE) experiments were performed, and the thermodynamic consistency of the data was rigorously validated. The NRTL model correlated well with the experimental VLE results. Quantum chemical calculations further revealed that the ILs break the azeotrope by restructuring the molecular interaction network, a process driven by enhanced hydrogen bonding. Process simulation confirmed the industrial feasibility of using [N1111][Ac] as an entrainer, which exhibited the highest separation efficiency, requiring only an IL molar fraction of 0.0385 to eliminate the azeotrope. Optimized process conditions showed that using [N1111][Ac] led to a 20.09% reduction in the total annual cost and a 26.05% decrease in gas emissions (CO2, SO2, and NOx) compared to conventional organic solvent DMSO, aligning with the principles of green chemistry. Both experimental and computational results confirm that these ILs are efficient and environmentally benign entrainers for IPA-water separation. The integrated methodology established in this work provides a robust framework for designing sustainable separation processes.
{"title":"Multiscale Investigation of Ionic Liquid Extractive Distillation: Molecular-Level Exploration to Process Optimization for the iso-Propanol-Water Azeotrope","authors":"Dongxiang Zhang, Yuxuan Xiao, Yue Wang, Meijun Wu, Hua Xin, Qinqin Zhang, Zhigang Zhang","doi":"10.1021/acs.iecr.5c04830","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04830","url":null,"abstract":"The separation of the <i>iso</i>-propanol (IPA)-water azeotrope is a significant challenge in the chemical and biomedical industries, primarily due to strong hydrogen bonding interactions that hinder conventional distillation. Although extractive distillation offers a viable solution, conventional entrainers suffer from limitations such as corrosion, volatility, and environmental issues. Ionic liquids (ILs) have emerged as promising green alternatives owing to their negligible vapor pressure, high thermal stability, and tunable properties. In this study, three acetate-based ammonium ILs─[N<sub>1111</sub>][Ac], [N<sub>2111</sub>][Ac], and [N<sub>4111</sub>][Ac]─were systematically screened using the COSMO-RS model. Isobaric vapor–liquid equilibrium (VLE) experiments were performed, and the thermodynamic consistency of the data was rigorously validated. The NRTL model correlated well with the experimental VLE results. Quantum chemical calculations further revealed that the ILs break the azeotrope by restructuring the molecular interaction network, a process driven by enhanced hydrogen bonding. Process simulation confirmed the industrial feasibility of using [N<sub>1111</sub>][Ac] as an entrainer, which exhibited the highest separation efficiency, requiring only an IL molar fraction of 0.0385 to eliminate the azeotrope. Optimized process conditions showed that using [N<sub>1111</sub>][Ac] led to a 20.09% reduction in the total annual cost and a 26.05% decrease in gas emissions (CO<sub>2</sub>, SO<sub>2</sub>, and NO<sub><i>x</i></sub>) compared to conventional organic solvent DMSO, aligning with the principles of green chemistry. Both experimental and computational results confirm that these ILs are efficient and environmentally benign entrainers for IPA-water separation. The integrated methodology established in this work provides a robust framework for designing sustainable separation processes.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"197 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490117","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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