Benzoyl peroxide (BPO), a widely used diacyl peroxide, is typically synthesized via heterogeneous peroxidation of benzoyl chloride (BC) and H2O2 in batch reactors—a process that suffers from low space–time yields and safety concerns. This study developed a safe and efficient continuous-flow synthesis using packed-bed microreactors. Importantly, a kinetic model coupling intrinsic reaction kinetics and mass transfer was established and validated across different packing sizes, providing mechanistic insight into the heterogeneous liquid–liquid process. The main reaction followed a slow regime governed by both kinetics and mass transfer, whereas the hydrolysis side reaction occurred in a very slow regime with negligible mass transfer resistance. Consequently, packed-bed microreactors enhanced mass transfer and improved BPO selectivity. Under optimal conditions (NaOH/BC = 1.0, H2O2/BC = 0.6, 50°C), a 94.4% BPO yield was achieved within 120 s. The space–time yield was over 51 times that of batch reactors. This study offers insights for intensifying and scaling up diacyl peroxide syntheses.
{"title":"Heterogeneous peroxidation of benzoyl chloride with H2O2 in packed-bed microreactors: Reaction regime and kinetics","authors":"Yuyang Xu, Rao Chen, Mei Yang, Lixia Yang, Shuainan Zhao, Chaoqun Yao, Guangwen Chen","doi":"10.1002/aic.70196","DOIUrl":"https://doi.org/10.1002/aic.70196","url":null,"abstract":"Benzoyl peroxide (BPO), a widely used diacyl peroxide, is typically synthesized via heterogeneous peroxidation of benzoyl chloride (BC) and H<sub>2</sub>O<sub>2</sub> in batch reactors—a process that suffers from low space–time yields and safety concerns. This study developed a safe and efficient continuous-flow synthesis using packed-bed microreactors. Importantly, a kinetic model coupling intrinsic reaction kinetics and mass transfer was established and validated across different packing sizes, providing mechanistic insight into the heterogeneous liquid–liquid process. The main reaction followed a slow regime governed by both kinetics and mass transfer, whereas the hydrolysis side reaction occurred in a very slow regime with negligible mass transfer resistance. Consequently, packed-bed microreactors enhanced mass transfer and improved BPO selectivity. Under optimal conditions (NaOH/BC = 1.0, H<sub>2</sub>O<sub>2</sub>/BC = 0.6, 50°C), a 94.4% BPO yield was achieved within 120 s. The space–time yield was over 51 times that of batch reactors. This study offers insights for intensifying and scaling up diacyl peroxide syntheses.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"36 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728747","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}
We address the identification of the actual stoichiometric network in reacting systems using composition measurements, extending our previous work (Fromer et al. I&ECR 2023). We generalize this algorithm for scenarios where not all species are measured and back‐calculate the missing concentrations through the reaction extents of the candidate network. In addition to the prior global accuracy comparison among candidate reaction networks, we introduce a species‐by‐species F ‐test accuracy comparison between the most accurate reaction networks from the global assessment. We examine two case studies involving 7 and 11 species participate in 4 or 8 reactions, respectively. In the second case study, the 8 reactions are linearly dependent, presenting an additional challenge. The enhanced algorithm successfully identifies the actual reaction network as the most accurate, even with 4 of the 11 species not measured.
{"title":"Stoichiometry model identification for homogeneous reaction mixture: High‐dimension and missing measurement case studies","authors":"Yafeng Xing, Yachao Dong, Christos Georgakis, Aaron Gould","doi":"10.1002/aic.70183","DOIUrl":"https://doi.org/10.1002/aic.70183","url":null,"abstract":"We address the identification of the actual stoichiometric network in reacting systems using composition measurements, extending our previous work (Fromer et al. I&ECR 2023). We generalize this algorithm for scenarios where not all species are measured and back‐calculate the missing concentrations through the reaction extents of the candidate network. In addition to the prior global accuracy comparison among candidate reaction networks, we introduce a species‐by‐species <jats:italic>F</jats:italic> ‐test accuracy comparison between the most accurate reaction networks from the global assessment. We examine two case studies involving 7 and 11 species participate in 4 or 8 reactions, respectively. In the second case study, the 8 reactions are linearly dependent, presenting an additional challenge. The enhanced algorithm successfully identifies the actual reaction network as the most accurate, even with 4 of the 11 species not measured.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"6 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711150","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}
Qiangbing Shi, Kaige Jia, Xiangping Zhang, Chuan Wang, Paul Cobden, Anna-Maria Beregi Amnéus, David Muren, Xiaoyan Ji
The development of advanced absorbents for effectively capturing carbon dioxide is crucial in mitigating greenhouse gas emissions. This study introduced a series of deep eutectic solvents (DESs) for CO2 capture and identified the most promising DESs with the stepwise screening method based on their absorption capacity, absorption rate, thermal stability, desorption efficiency, and apparent activation energy. Consequently, compared to the monoethanolamine (MEA), in the 30 wt% aqueous solutions, [1,2,3-Triazolium chloride][diethylenetriamine] ([TrizCl][DETA]) and [Piperazinium chloride][diethylenetriamine] ([PzCl][DETA]) improved the CO2 absorption capacities by 31% and 34%, absorption rates by 12% and 30%, and the amounts of CO2 desorbed by 42% and 23%, as well as reduced the apparent activation energies by 9% and 28%, respectively. Meanwhile, their thermal stabilities (degradation onset temperatures, Tonset) were enhanced by 101% and 32%, respectively. The FTIR and NMR analyses were conducted to provide deeper insights into the chemical absorption mechanism of CO2 by the DESs.
{"title":"Development and systematic evaluation of triamine-based functional deep eutectic solvents for efficient CO2 capture","authors":"Qiangbing Shi, Kaige Jia, Xiangping Zhang, Chuan Wang, Paul Cobden, Anna-Maria Beregi Amnéus, David Muren, Xiaoyan Ji","doi":"10.1002/aic.70184","DOIUrl":"https://doi.org/10.1002/aic.70184","url":null,"abstract":"The development of advanced absorbents for effectively capturing carbon dioxide is crucial in mitigating greenhouse gas emissions. This study introduced a series of deep eutectic solvents (DESs) for CO<sub>2</sub> capture and identified the most promising DESs with the stepwise screening method based on their absorption capacity, absorption rate, thermal stability, desorption efficiency, and apparent activation energy. Consequently, compared to the monoethanolamine (MEA), in the 30 wt% aqueous solutions, [1,2,3-Triazolium chloride][diethylenetriamine] ([TrizCl][DETA]) and [Piperazinium chloride][diethylenetriamine] ([PzCl][DETA]) improved the CO<sub>2</sub> absorption capacities by 31% and 34%, absorption rates by 12% and 30%, and the amounts of CO<sub>2</sub> desorbed by 42% and 23%, as well as reduced the apparent activation energies by 9% and 28%, respectively. Meanwhile, their thermal stabilities (degradation onset temperatures, <i>T</i><sub>onset</sub>) were enhanced by 101% and 32%, respectively. The FTIR and NMR analyses were conducted to provide deeper insights into the chemical absorption mechanism of CO<sub>2</sub> by the DESs.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"8 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718462","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}
Liquid–liquid interfacial polymerization (IP) serves as a facile method for fabricating covalent organic framework (COF) membranes, while designing task‐specific IP systems remains a huge challenge. This work proposes a rational strategy to achieve controlled IP by monomer–catalyst–biphasic solvents matching, integrating thermodynamic predictions and dynamic insights. For the IP engineering, ionic liquids (ILs) are introduced into the biphasic solvent system due to their unique physicochemical properties. Utilizing conductor‐like screening model for realistic solvents (COSMO‐RS) calculations, deep learning‐aided physical properties predictions, and molecular dynamics simulations, 10 promising pairs were identified from 622 candidates. This strategy enables the transition from highly cross‐linked amorphous membranes to uniform crystalline membranes with reduced thickness (from 520 to 124 nm), synergizing thermodynamic partition and diffusion regulation. The membranes exhibit increased water permeance (from 0.022 to 7.43 L·m −2 ·h −1 ·bar −1 ) and high antibiotic desalination efficiency. Furthermore, this strategy is successfully extended to other COF membranes, enriching the tuning flexibility of IP system for the development of novel COF membranes.
{"title":"Rationally engineering interfacial polymerization toward covalent organic framework membranes mediated by ionic liquids","authors":"Ke Wang, Wei Cao, Kunchi Xie, Shuyun Gu, Siyao Li, Zhiwen Qi, Zhen Song, Zhi Xu","doi":"10.1002/aic.70186","DOIUrl":"https://doi.org/10.1002/aic.70186","url":null,"abstract":"Liquid–liquid interfacial polymerization (IP) serves as a facile method for fabricating covalent organic framework (COF) membranes, while designing task‐specific IP systems remains a huge challenge. This work proposes a rational strategy to achieve controlled IP by monomer–catalyst–biphasic solvents matching, integrating thermodynamic predictions and dynamic insights. For the IP engineering, ionic liquids (ILs) are introduced into the biphasic solvent system due to their unique physicochemical properties. Utilizing conductor‐like screening model for realistic solvents (COSMO‐RS) calculations, deep learning‐aided physical properties predictions, and molecular dynamics simulations, 10 promising pairs were identified from 622 candidates. This strategy enables the transition from highly cross‐linked amorphous membranes to uniform crystalline membranes with reduced thickness (from 520 to 124 nm), synergizing thermodynamic partition and diffusion regulation. The membranes exhibit increased water permeance (from 0.022 to 7.43 L·m <jats:sup>−2</jats:sup> ·h <jats:sup>−1</jats:sup> ·bar <jats:sup>−1</jats:sup> ) and high antibiotic desalination efficiency. Furthermore, this strategy is successfully extended to other COF membranes, enriching the tuning flexibility of IP system for the development of novel COF membranes.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"77 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704157","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}
Partial hydrogenolysis of dimethyl oxalate (DMO) to methyl glycolate (MG) is a central step in biodegradable polyglycolic acid (PGA) production. However, it remains a great challenge for efficient and selective DMO hydrogenolysis under mild temperature (<100°C). In this work, we demonstrate an outstanding DMO hydrogenolysis by employing alkaline (Na, K) metal-doped Ru catalysts. Na presents a stronger promotional effect than K. The highest yield of MG is achieved at 90.2% at 85°C in 15 h of reaction on 3Ru-0.4Na/SiO2 and the catalyst can be directly reused more than 10 times without any additional regeneration. The doping of Na effectively enables smaller Ru nanoparticle size, larger capacity of H2 adsorption via a hydrogen pool (includes surface hydride, i.e., Na-Hδ−) on Ru–Na interface, stronger strength of DMO adsorption. It is further revealed that there is a linear relation between the content of surface Ru0 + Ru3+ + Ruδ− and MG yield. Finally, an optimal ratio of Ru3+ + Ruδ−/Ru0 of 1.26 is achieved.
{"title":"Engineering Ru-based catalysts via cooperating with alkaline metals for partial hydrogenolysis of dimethyl oxalate","authors":"Xin Gao, Han-Xuan Liu, Donghui Xiao, Shilong Xie, Riguang Zhang, Chun-Ran Chang","doi":"10.1002/aic.70172","DOIUrl":"https://doi.org/10.1002/aic.70172","url":null,"abstract":"Partial hydrogenolysis of dimethyl oxalate (DMO) to methyl glycolate (MG) is a central step in biodegradable polyglycolic acid (PGA) production. However, it remains a great challenge for efficient and selective DMO hydrogenolysis under mild temperature (<100°C). In this work, we demonstrate an outstanding DMO hydrogenolysis by employing alkaline (Na, K) metal-doped Ru catalysts. Na presents a stronger promotional effect than K. The highest yield of MG is achieved at 90.2% at 85°C in 15 h of reaction on 3Ru-0.4Na/SiO<sub>2</sub> and the catalyst can be directly reused more than 10 times without any additional regeneration. The doping of Na effectively enables smaller Ru nanoparticle size, larger capacity of H<sub>2</sub> adsorption via a hydrogen pool (includes surface hydride, i.e., Na-H<sup><i>δ</i>−</sup>) on Ru–Na interface, stronger strength of DMO adsorption. It is further revealed that there is a linear relation between the content of surface Ru<sup>0</sup> + Ru<sup>3+</sup> + Ru<sup><i>δ</i>−</sup> and MG yield. Finally, an optimal ratio of Ru<sup>3+</sup> + Ru<sup><i>δ</i>−</sup>/Ru<sup>0</sup> of 1.26 is achieved.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"2 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711532","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}
Combining CO 2 capture with sustainable salt recovery in biofuel production is a promising strategy to address environmental and economic challenges in biorefinery. This study demonstrates a closed‐loop system that utilizes K 2 CO 3 as a bifunctional agent for both separation and purification of acetone–1‐butanol–ethanol (ABE) solution and CO 2 capture from biofuel fermentation. Salt reuse and CO 2 sequestration were achieved by reacting CO 2 with salted K 2 CO 3 ‐rich aqueous phase to form KHCO 3 . The experimental results showed that K 2 CO 3 could achieve efficient ABE separation (>99% recovery of 1‐butanol at 500 g/kg) and CO 2 utilization reached 88% under optimal conditions (stirring rate of 1100 r/min, gas flow rate of 40 mL/min). Salt recovery stabilized at 84%, which was limited by KHCO 3 solubility and ionic strength. This research provides a scalable blueprint for sustainable biofuel production by addressing the twin challenges of resource waste and carbon emissions.
{"title":"Integration of biofuel extraction and biorefinery carbon dioxide capture for closed‐loop salt recycling to reduce carbon emission","authors":"Rongze Lin, Linjing Zhong, Fulin Hu, Zixuan Tan, Ziyi Ma, Zidi Liu, Shaoqu Xie","doi":"10.1002/aic.70180","DOIUrl":"https://doi.org/10.1002/aic.70180","url":null,"abstract":"Combining CO <jats:sub>2</jats:sub> capture with sustainable salt recovery in biofuel production is a promising strategy to address environmental and economic challenges in biorefinery. This study demonstrates a closed‐loop system that utilizes K <jats:sub>2</jats:sub> CO <jats:sub>3</jats:sub> as a bifunctional agent for both separation and purification of acetone–1‐butanol–ethanol (ABE) solution and CO <jats:sub>2</jats:sub> capture from biofuel fermentation. Salt reuse and CO <jats:sub>2</jats:sub> sequestration were achieved by reacting CO <jats:sub>2</jats:sub> with salted K <jats:sub>2</jats:sub> CO <jats:sub>3</jats:sub> ‐rich aqueous phase to form KHCO <jats:sub>3</jats:sub> . The experimental results showed that K <jats:sub>2</jats:sub> CO <jats:sub>3</jats:sub> could achieve efficient ABE separation (>99% recovery of 1‐butanol at 500 g/kg) and CO <jats:sub>2</jats:sub> utilization reached 88% under optimal conditions (stirring rate of 1100 r/min, gas flow rate of 40 mL/min). Salt recovery stabilized at 84%, which was limited by KHCO <jats:sub>3</jats:sub> solubility and ionic strength. This research provides a scalable blueprint for sustainable biofuel production by addressing the twin challenges of resource waste and carbon emissions.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"239 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704542","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}
Fanyu Wang, Zhongsen Wang, Qian Zhu, Jintong Lan, Yi Liu, Xiao Liu
Enhancing low‐temperature activity of metal oxides in gas‐solid catalysis remains a significant challenge. Here, we propose a single‐atom niobium (Nb) regulation strategy to optimize the d‐electron structure of manganese in MnO 2 catalysts for 200 ppm formaldehyde oxidation with 37.5% relative humidity. The Nb‐doped MnO 2 demonstrates remarkable catalytic performance, lowering T 90 (the temperature at which 90% conversion is reached) by 42 °C compared to undoped MnO 2 . This enhancement originates from directional control of d‐orbital splitting energy and optimized eg orbital filling of Mn, which collectively reduces the electron‐transfer barrier during the reaction. In situ characterization and DFT calculation also reveal a synergistic adsorption configuration where HCHO and H 2 O molecules form an electron relay transfer network. Our work establishes atomic‐level electronic structure engineering as an effective approach to improve catalytic efficiency, while the identified electron relay mechanism provides fundamental insights into the metal oxide interface interactions for heterogeneous catalytic systems.
{"title":"Optimized e g orbitals of Mn enable H 2 O activation for low‐temperature HCHO oxidation over atomically Nb‐doped MnO 2 ","authors":"Fanyu Wang, Zhongsen Wang, Qian Zhu, Jintong Lan, Yi Liu, Xiao Liu","doi":"10.1002/aic.70188","DOIUrl":"https://doi.org/10.1002/aic.70188","url":null,"abstract":"Enhancing low‐temperature activity of metal oxides in gas‐solid catalysis remains a significant challenge. Here, we propose a single‐atom niobium (Nb) regulation strategy to optimize the d‐electron structure of manganese in MnO <jats:sub>2</jats:sub> catalysts for 200 ppm formaldehyde oxidation with 37.5% relative humidity. The Nb‐doped MnO <jats:sub>2</jats:sub> demonstrates remarkable catalytic performance, lowering T <jats:sub>90</jats:sub> (the temperature at which 90% conversion is reached) by 42 °C compared to undoped MnO <jats:sub>2</jats:sub> . This enhancement originates from directional control of d‐orbital splitting energy and optimized <jats:italic>e</jats:italic> <jats:sub> <jats:italic>g</jats:italic> </jats:sub> orbital filling of Mn, which collectively reduces the electron‐transfer barrier during the reaction. In situ characterization and DFT calculation also reveal a synergistic adsorption configuration where HCHO and H <jats:sub>2</jats:sub> O molecules form an electron relay transfer network. Our work establishes atomic‐level electronic structure engineering as an effective approach to improve catalytic efficiency, while the identified electron relay mechanism provides fundamental insights into the metal oxide interface interactions for heterogeneous catalytic systems.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"93 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704152","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}
Lichao Li, Tongrui Shao, Yang Su, Xiaodong Wang, Jian Lin
Water gas shift (WGS) reaction is crucial for removing CO impurity in industrial hydrogen production. Noble-metal-free Co-based species mainly serve as a support rather than dominant sites for this reaction. Here, a bulk Co4N nanospheres (Co4N-NS) catalyst is prepared via temperature programmed nitriding using Co3O4 nanosphere precursor for low-temperature WGS reaction. It is found that the CO conversion can achieve 97.6% at 240°C, and the thermodynamic equilibrium conversion is reached at 250°C, which is unprecedentedly reported for Co-based catalysts. Moreover, the reaction rate reaches 19.84 mmolCO gcat−1 h−1 with a better stability, 4.5 times higher than that on Co4N-C from commercial Co3O4 precursor. The characterizations and kinetic studies show that Co4N-NS enhances the H2O activation and promotes the CO adsorption, which renders a lower activation energy compared to Co4N-C for the WGS reaction. This study offers insights for designing cost-effective WGS catalysts with transition metal nitrides.
{"title":"Noble-metal-free Co4N derived from Co3O4 nanosphere as an effective catalyst for water gas shift reaction","authors":"Lichao Li, Tongrui Shao, Yang Su, Xiaodong Wang, Jian Lin","doi":"10.1002/aic.70179","DOIUrl":"https://doi.org/10.1002/aic.70179","url":null,"abstract":"Water gas shift (WGS) reaction is crucial for removing CO impurity in industrial hydrogen production. Noble-metal-free Co-based species mainly serve as a support rather than dominant sites for this reaction. Here, a bulk Co<sub>4</sub>N nanospheres (Co<sub>4</sub>N-NS) catalyst is prepared via temperature programmed nitriding using Co<sub>3</sub>O<sub>4</sub> nanosphere precursor for low-temperature WGS reaction. It is found that the CO conversion can achieve 97.6% at 240°C, and the thermodynamic equilibrium conversion is reached at 250°C, which is unprecedentedly reported for Co-based catalysts. Moreover, the reaction rate reaches 19.84 mmol<sub>CO</sub> g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup> with a better stability, 4.5 times higher than that on Co<sub>4</sub>N-C from commercial Co<sub>3</sub>O<sub>4</sub> precursor. The characterizations and kinetic studies show that Co<sub>4</sub>N-NS enhances the H<sub>2</sub>O activation and promotes the CO adsorption, which renders a lower activation energy compared to Co<sub>4</sub>N-C for the WGS reaction. This study offers insights for designing cost-effective WGS catalysts with transition metal nitrides.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"93 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729229","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}
Qi Liu, Yan Ouyang, Tong Luo, Qinlan Luo, Min Xiao, Hongxia Gao, Zhiwu Liang
Blending is a common method to improve the performance of amine solution for CO 2 capture. While the amine will degrade at elevated temperatures or so‐called thermal degradation, the mixing of multiple amines could change the thermal degradation behavior and it is critical to reveal them before implementing the CO 2 capture at large scale. Herein, the thermal degradation performance of blended amines was studied via experimental and computational methods. In comparison with single amine solution, the effect of an additional tertiary amine N,N ‐dimethylethanolamine (DMEA) was analyzed. The thermal degradation experiments were carried out at multiple temperatures. The temperature threshold was identified for the blended solution after which the degradation rate increases dramatically. Based on the obtained degradation products, the degradation mechanism of the blended amine is proposed. The energy barrier of key reactions in thermal degradation was obtained and the interaction of primary amine and tertiary amine is clarified.
{"title":"Thermal degradation of primary amines blended with N , N ‐dimethylethanolamine in post‐combustion carbon capture","authors":"Qi Liu, Yan Ouyang, Tong Luo, Qinlan Luo, Min Xiao, Hongxia Gao, Zhiwu Liang","doi":"10.1002/aic.70178","DOIUrl":"https://doi.org/10.1002/aic.70178","url":null,"abstract":"Blending is a common method to improve the performance of amine solution for CO <jats:sub>2</jats:sub> capture. While the amine will degrade at elevated temperatures or so‐called thermal degradation, the mixing of multiple amines could change the thermal degradation behavior and it is critical to reveal them before implementing the CO <jats:sub>2</jats:sub> capture at large scale. Herein, the thermal degradation performance of blended amines was studied via experimental and computational methods. In comparison with single amine solution, the effect of an additional tertiary amine <jats:italic>N,N</jats:italic> ‐dimethylethanolamine (DMEA) was analyzed. The thermal degradation experiments were carried out at multiple temperatures. The temperature threshold was identified for the blended solution after which the degradation rate increases dramatically. Based on the obtained degradation products, the degradation mechanism of the blended amine is proposed. The energy barrier of key reactions in thermal degradation was obtained and the interaction of primary amine and tertiary amine is clarified.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"44 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704153","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}
Electrocatalytic propylene oxidation to 1,2‐propylene glycol (PG) offers advantages over thermocatalytic routes through milder reaction conditions and concomitant green hydrogen production. Diverging from conventional palladium oxide paradigms, for the first time we demonstrate hollow nanosphere Pd 17 Se 15 and Pd 7 Se 4 exhibiting phase‐dependent reactivity for propylene electrooxidation to PG. Pd 17 Se 15 presents superior selectivity and Faradaic efficiency for PG compared to Pd 7 Se 4 and achieves twice the PG Faradaic efficiency of commercial Pd/C, owing to its distinctive crystal phase and local coordination environments. In situ attenuated total reflection Fourier transform infrared spectroscopy with isotopic labeling reveals that enhanced performance originates from optimized propylene adsorption energetics and accelerated *OH generation via efficient water activation. Density functional theory calculations confirm that Pd 17 Se 15 facilitates propylene adsorption and exhibits lower energy barriers for sequential hydroxylation than Pd 7 Se 4 . This study establishes the Pd‐Se phase‐dependent correlation in propylene electrooxidation to PG and advances the sustainable electrochemical upgrading strategy of light olefins.
{"title":"Crystal phase modulation of Pd‐Se hollow nanospheres for selective propylene electrooxidation to propylene glycol","authors":"Weizhong Liao, Wei Yan, Zhiyong Yu, Peidie Fang, Qingyu Kong, Jihao Zhang, Zhiwei Hu, Haixin Lin, Dazhi Shen, Xiaoqing Huang, Yunhua Li","doi":"10.1002/aic.70190","DOIUrl":"https://doi.org/10.1002/aic.70190","url":null,"abstract":"Electrocatalytic propylene oxidation to 1,2‐propylene glycol (PG) offers advantages over thermocatalytic routes through milder reaction conditions and concomitant green hydrogen production. Diverging from conventional palladium oxide paradigms, for the first time we demonstrate hollow nanosphere Pd <jats:sub>17</jats:sub> Se <jats:sub>15</jats:sub> and Pd <jats:sub>7</jats:sub> Se <jats:sub>4</jats:sub> exhibiting phase‐dependent reactivity for propylene electrooxidation to PG. Pd <jats:sub>17</jats:sub> Se <jats:sub>15</jats:sub> presents superior selectivity and Faradaic efficiency for PG compared to Pd <jats:sub>7</jats:sub> Se <jats:sub>4</jats:sub> and achieves twice the PG Faradaic efficiency of commercial Pd/C, owing to its distinctive crystal phase and local coordination environments. <jats:italic>In situ</jats:italic> attenuated total reflection Fourier transform infrared spectroscopy with isotopic labeling reveals that enhanced performance originates from optimized propylene adsorption energetics and accelerated *OH generation via efficient water activation. Density functional theory calculations confirm that Pd <jats:sub>17</jats:sub> Se <jats:sub>15</jats:sub> facilitates propylene adsorption and exhibits lower energy barriers for sequential hydroxylation than Pd <jats:sub>7</jats:sub> Se <jats:sub>4</jats:sub> . This study establishes the Pd‐Se phase‐dependent correlation in propylene electrooxidation to PG and advances the sustainable electrochemical upgrading strategy of light olefins.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"20 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145697161","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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