Pub Date : 2025-12-01Epub Date: 2025-07-01DOI: 10.1016/j.gce.2025.06.008
Haichuan Yin , Yan Xu , Xiaochun Zhang , Xu Wang , Peng Yang , Guoxiong Zhan , Yinge Bai , Zhenlei Zhang , Xiangping Zhang
The urgent need to mitigate anthropogenic CO2 emissions has driven the development of energy-efficient carbon capture systems. This study investigated a [N1111][Triz]-H2O hybrid solvent for CO2 capture using integrated experimental and computational approaches. A multiscale methodology combining thermodynamic analysis, phase equilibrium measurements, and molecular dynamics (MD) simulations was employed to elucidate the absorption mechanisms and the composition-property relationships. The thermodynamic analysis, incorporating Henry's law, the non-random two-liquid (NRTL) model for activity coefficients, the Redlich-Kwong equation, and reaction equilibrium constraints, accurately predicted the gas-liquid equilibrium (GLE) behavior, achieving an R2 of 99.1% and an average absolute relative deviation (AARD) of 7.76%. The [N1111][Triz]-H2O hybrid solvent exhibits exceptional CO2 absorption performance, with a capacity of 0.25 mol/mol (at 313.15 K and 0.025 MPa for wIL = 80%), attributed to synergistic physical-chemical interactions. MD simulations reveal the dynamic CO2 absorption process in [N1111][Triz]-H2O hybrid solvents: CO2 molecules preferentially accumulate at the gas-liquid interface before gradually diffusing into the bulk phase. Increasing the [N1111][Triz] content enhances CO2 absorption capacity by providing more interaction sites, while water modulates interfacial behavior and diffusion kinetics. This research provides in-depth insights into the absorption behaviors of [N1111][Triz]-H2O hybrid solvents for CO2, offering theoretical support for the development of efficient CO2 capture solvents and highlighting its potential for industrial implementation.
{"title":"A multiscale investigation combining thermodynamic modeling and molecular dynamics study on CO2 capture with [N1111][Triz]-H2O solvent","authors":"Haichuan Yin , Yan Xu , Xiaochun Zhang , Xu Wang , Peng Yang , Guoxiong Zhan , Yinge Bai , Zhenlei Zhang , Xiangping Zhang","doi":"10.1016/j.gce.2025.06.008","DOIUrl":"10.1016/j.gce.2025.06.008","url":null,"abstract":"<div><div>The urgent need to mitigate anthropogenic CO<sub>2</sub> emissions has driven the development of energy-efficient carbon capture systems. This study investigated a [N<sub>1111</sub>][Triz]-H<sub>2</sub>O hybrid solvent for CO<sub>2</sub> capture using integrated experimental and computational approaches. A multiscale methodology combining thermodynamic analysis, phase equilibrium measurements, and molecular dynamics (MD) simulations was employed to elucidate the absorption mechanisms and the composition-property relationships. The thermodynamic analysis, incorporating Henry's law, the non-random two-liquid (NRTL) model for activity coefficients, the Redlich-Kwong equation, and reaction equilibrium constraints, accurately predicted the gas-liquid equilibrium (GLE) behavior, achieving an R<sup>2</sup> of 99.1% and an average absolute relative deviation (AARD) of 7.76%. The [N<sub>1111</sub>][Triz]-H<sub>2</sub>O hybrid solvent exhibits exceptional CO<sub>2</sub> absorption performance, with a capacity of 0.25 mol/mol (at 313.15 K and 0.025 MPa for <em>w</em><sub>IL</sub> = 80%), attributed to synergistic physical-chemical interactions. MD simulations reveal the dynamic CO<sub>2</sub> absorption process in [N<sub>1111</sub>][Triz]-H<sub>2</sub>O hybrid solvents: CO<sub>2</sub> molecules preferentially accumulate at the gas-liquid interface before gradually diffusing into the bulk phase. Increasing the [N<sub>1111</sub>][Triz] content enhances CO<sub>2</sub> absorption capacity by providing more interaction sites, while water modulates interfacial behavior and diffusion kinetics. This research provides in-depth insights into the absorption behaviors of [N<sub>1111</sub>][Triz]-H<sub>2</sub>O hybrid solvents for CO<sub>2</sub>, offering theoretical support for the development of efficient CO<sub>2</sub> capture solvents and highlighting its potential for industrial implementation.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"6 4","pages":"Pages 591-599"},"PeriodicalIF":7.6,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144917739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Heterogeneous catalysts, particularly shaped catalysts, could be directly packed into continuous industrial reactors and offer advantages such as easy separation and environmental friendliness, making them ideal for sustainable industrial production. However, the internal mass-transfer limitations of shaped particles and the poor accessibility of active sites often restrict their catalytic performance. In this work, highly active ionic sites were incorporated directly into shaped polymers to impart flexible adsorption capabilities, and through simple particle-size control, both internal and external active sites were fully utilized, yielding shaped catalysts that combine high activity with excellent stability toward the transesterification reaction of dimethyl carbonate with ethanol. Systematic studies revealed a particle-size-dependent activity profile, where optimal performance balanced external diffusion and swelling confinement. Under batch conditions (90 °C, 4 h, 7 wt% catalyst), ethyl methyl carbonate (EMC) yield reached 50.83% with 96.25% selectivity, surpassing reported heterogeneous catalysts. The catalyst exhibited exceptional stability over five regeneration cycles and continuous operation for 2400 h in a fixed-bed reactor (85 °C, 1 h residence time) without performance decay or pressure drop. This work demonstrates that shaped flexible catalysts synergize industrial process compatibility with high activity and durability, offering a sustainable route for EMC production. • A directly shaped flexible ionic polymer (PVD- x ) was developed for EMC synthesis; • Shaped PVD- x could be directly applied in industrial continuous catalytic units; • PVD- x provided recyclable, sustainable alternative to sodium methoxide in industry; • PVD- x delivered excellent performance with EMC 50.83% yield, 96.25% selectivity; • PVD- x maintained stability for over 2400 h in continuous fixed-bed operation; • DFT revealed the mechanism by which adsorption enhances catalytic activity.
{"title":"Size-controlled flexible ionic polymer catalysts with enhanced mass transfer for sustainable ethyl methyl carbonate production","authors":"Rongkai Cui, Miaomiao Cui, Fuying Zhang, Xiaoyan Chen, Ting Qiu, Jie Chen","doi":"10.1016/j.gce.2025.11.001","DOIUrl":"https://doi.org/10.1016/j.gce.2025.11.001","url":null,"abstract":"Heterogeneous catalysts, particularly shaped catalysts, could be directly packed into continuous industrial reactors and offer advantages such as easy separation and environmental friendliness, making them ideal for sustainable industrial production. However, the internal mass-transfer limitations of shaped particles and the poor accessibility of active sites often restrict their catalytic performance. In this work, highly active ionic sites were incorporated directly into shaped polymers to impart flexible adsorption capabilities, and through simple particle-size control, both internal and external active sites were fully utilized, yielding shaped catalysts that combine high activity with excellent stability toward the transesterification reaction of dimethyl carbonate with ethanol. Systematic studies revealed a particle-size-dependent activity profile, where optimal performance balanced external diffusion and swelling confinement. Under batch conditions (90 °C, 4 h, 7 wt% catalyst), ethyl methyl carbonate (EMC) yield reached 50.83% with 96.25% selectivity, surpassing reported heterogeneous catalysts. The catalyst exhibited exceptional stability over five regeneration cycles and continuous operation for 2400 h in a fixed-bed reactor (85 °C, 1 h residence time) without performance decay or pressure drop. This work demonstrates that shaped flexible catalysts synergize industrial process compatibility with high activity and durability, offering a sustainable route for EMC production. • A directly shaped flexible ionic polymer (PVD- x ) was developed for EMC synthesis; • Shaped PVD- x could be directly applied in industrial continuous catalytic units; • PVD- x provided recyclable, sustainable alternative to sodium methoxide in industry; • PVD- x delivered excellent performance with EMC 50.83% yield, 96.25% selectivity; • PVD- x maintained stability for over 2400 h in continuous fixed-bed operation; • DFT revealed the mechanism by which adsorption enhances catalytic activity.","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332137","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01Epub Date: 2024-09-16DOI: 10.1016/j.gce.2024.09.006
Enze Li , Jing Dong , Yongsheng Jia , Zihe Pan , Hongzhou Lv , Zhiping Du , Guandao Gao , Fangqin Cheng
Sufficient treatment of industrial organic wastewater with high salt and large amounts of suspended particulate matter remains a challenge worldwide. In this work, a novel coagulation-flotation combined process was developed to treat the suspended particles as well as significantly reduce organic pollutants content in the actual high-salt organic wastewater. Four typical inorganic and organic flocculants (poly aluminum chloride (PAC), poly ferric sulfate (PFS), polyacrylamide (PAM), and modified cationic starch (CS)) were selected for compounding to obtain an optimized flocculation system for high-salt wastewater. The results showed that the PAC-PAM with a 10:1 ratio in mass exhibited the best coagulation behaviors with the removal efficiency of turbidity and chemical oxygen demand (COD) being 95.33% and 9.21%, respectively, under the optimal operation conditions, and the sedimentation process of coagulant conformed to the quasi-second-order kinetics. The PAC-PAM flocs exhibited stronger netting, sweeping, and adsorption bridging capabilities, which were conducive to removing suspended particles. When the flotation was conducted after coagulation, the COD decreased significantly by 20.82%. In addition, this combined process could reduce the treatment time by 50% compared to the process with only coagulation treatment. During the flotation process, floc particles companies with hydrophobic polycyclic aromatic hydrocarbons could collide and adhere to microbubbles and be floated to the surface, resulting in an effective reduction of COD. This work could provide a novel strategy and step forward to design and optimize the pretreatment process engineering for organic high-salt wastewater.
{"title":"Synergistic enhancement of pollutant removal from high-salt wastewater using coagulation-flotation combined process","authors":"Enze Li , Jing Dong , Yongsheng Jia , Zihe Pan , Hongzhou Lv , Zhiping Du , Guandao Gao , Fangqin Cheng","doi":"10.1016/j.gce.2024.09.006","DOIUrl":"10.1016/j.gce.2024.09.006","url":null,"abstract":"<div><div>Sufficient treatment of industrial organic wastewater with high salt and large amounts of suspended particulate matter remains a challenge worldwide. In this work, a novel coagulation-flotation combined process was developed to treat the suspended particles as well as significantly reduce organic pollutants content in the actual high-salt organic wastewater. Four typical inorganic and organic flocculants (poly aluminum chloride (PAC), poly ferric sulfate (PFS), polyacrylamide (PAM), and modified cationic starch (CS)) were selected for compounding to obtain an optimized flocculation system for high-salt wastewater. The results showed that the PAC-PAM with a 10:1 ratio in mass exhibited the best coagulation behaviors with the removal efficiency of turbidity and chemical oxygen demand (COD) being 95.33% and 9.21%, respectively, under the optimal operation conditions, and the sedimentation process of coagulant conformed to the quasi-second-order kinetics. The PAC-PAM flocs exhibited stronger netting, sweeping, and adsorption bridging capabilities, which were conducive to removing suspended particles. When the flotation was conducted after coagulation, the COD decreased significantly by 20.82%. In addition, this combined process could reduce the treatment time by 50% compared to the process with only coagulation treatment. During the flotation process, floc particles companies with hydrophobic polycyclic aromatic hydrocarbons could collide and adhere to microbubbles and be floated to the surface, resulting in an effective reduction of COD. This work could provide a novel strategy and step forward to design and optimize the pretreatment process engineering for organic high-salt wastewater.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"6 3","pages":"Pages 410-419"},"PeriodicalIF":9.1,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144116663","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01Epub Date: 2024-09-26DOI: 10.1016/j.gce.2024.09.009
Mutawakkil Isah , Ridhwan Lawal , Sagheer A. Onaizi
Rapidly increasing global atmospheric carbon dioxide (CO2) concentration poses a serious threat to life on Earth. Conventional CO2 capture methodologies which rely on using sorbents to capture CO2 from point sources while effective in curbing the rate of CO2 increase, fall short of achieving net reduction. The last decade has witnessed a surge in the development of chemical sorbents cycled through adsorption-desorption processes for CO2 extraction from low-concentration sources like air (e.g., Direct Air Capture (DAC)). However, the efficiency of these technologies hinges on the creation of next-generation materials. Graphene, a revolutionary material discovered about two decades ago, offers great promise for CO2 capture and conversion. This single-atom-thick sheet of sp2-hybridized carbon atoms has unique and tuneable properties, solidifying its position as the most extensively studied nanomaterial of the 21st century. This review provides a comprehensive overview of the developing field of graphene-based materials for CO2 capture and conversion. The discussion begins with an exploration of the synthesis techniques for graphene and the integration of foreign elements to tune its properties for targeted applications. Subsequently, the review discusses the utilization of graphene and its derivatives in both CO2 capture and conversion processes, encompassing photocatalytic and electrocatalytic conversion methods. Despite the immense potential, the practical implementation of graphene-based DAC necessitates further exploration and development. Notably, engineering efficient of graphene-air interfacial contact is paramount to expediting the deployment of DAC as a viable strategy for mitigating climate change. The review concludes by highlighting gaps for future research to tackle challenges in this critical area of environmental pollution mitigation.
{"title":"CO2 capture and conversion using graphene-based materials: a review on recent progresses and future outlooks","authors":"Mutawakkil Isah , Ridhwan Lawal , Sagheer A. Onaizi","doi":"10.1016/j.gce.2024.09.009","DOIUrl":"10.1016/j.gce.2024.09.009","url":null,"abstract":"<div><div>Rapidly increasing global atmospheric carbon dioxide (CO<sub>2</sub>) concentration poses a serious threat to life on Earth. Conventional CO<sub>2</sub> capture methodologies which rely on using sorbents to capture CO<sub>2</sub> from point sources while effective in curbing the rate of CO<sub>2</sub> increase, fall short of achieving net reduction. The last decade has witnessed a surge in the development of chemical sorbents cycled through adsorption-desorption processes for CO<sub>2</sub> extraction from low-concentration sources like air (<em>e.g.</em>, Direct Air Capture (DAC)). However, the efficiency of these technologies hinges on the creation of next-generation materials. Graphene, a revolutionary material discovered about two decades ago, offers great promise for CO<sub>2</sub> capture and conversion. This single-atom-thick sheet of sp<sup>2</sup>-hybridized carbon atoms has unique and tuneable properties, solidifying its position as the most extensively studied nanomaterial of the 21<sup>st</sup> century. This review provides a comprehensive overview of the developing field of graphene-based materials for CO<sub>2</sub> capture and conversion. The discussion begins with an exploration of the synthesis techniques for graphene and the integration of foreign elements to tune its properties for targeted applications. Subsequently, the review discusses the utilization of graphene and its derivatives in both CO<sub>2</sub> capture and conversion processes, encompassing photocatalytic and electrocatalytic conversion methods. Despite the immense potential, the practical implementation of graphene-based DAC necessitates further exploration and development. Notably, engineering efficient of graphene-air interfacial contact is paramount to expediting the deployment of DAC as a viable strategy for mitigating climate change. The review concludes by highlighting gaps for future research to tackle challenges in this critical area of environmental pollution mitigation.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"6 3","pages":"Pages 305-334"},"PeriodicalIF":9.1,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144116666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01Epub Date: 2024-08-02DOI: 10.1016/j.gce.2024.08.001
Yuting Ruan , Yongtao Wang , Jia Yao , Haoran Li
Cyclohexylamine is a key byproduct during the production of cyclohexanone oxime, which is an important bulk chemical in material industry. Here we report a highly efficient approach to oxidize cyclohexylamine toward cyclohexanone with oxoammonium salt as the oxidant and water as the oxygen source, which has non-involvement of metal catalyst. The obtained cyclohexanone is an important raw material for both cyclohexanone oxime and adipic acid production. On basis of control experiments, mass spectrometry, and product analysis, the essential role of water as oxygen source and the reaction mechanism were elucidated. Moreover, the recycling of the oxoammonium salt succeeded to convert another proportion of the substrate. These findings offer new insights and methods for the oxidative conversion of cyclohexylamine.
{"title":"Oxoammonium salt mediated conversion of cyclohexylamine toward cyclohexanone with water as the oxygen source","authors":"Yuting Ruan , Yongtao Wang , Jia Yao , Haoran Li","doi":"10.1016/j.gce.2024.08.001","DOIUrl":"10.1016/j.gce.2024.08.001","url":null,"abstract":"<div><div>Cyclohexylamine is a key byproduct during the production of cyclohexanone oxime, which is an important bulk chemical in material industry. Here we report a highly efficient approach to oxidize cyclohexylamine toward cyclohexanone with oxoammonium salt as the oxidant and water as the oxygen source, which has non-involvement of metal catalyst. The obtained cyclohexanone is an important raw material for both cyclohexanone oxime and adipic acid production. On basis of control experiments, mass spectrometry, and product analysis, the essential role of water as oxygen source and the reaction mechanism were elucidated. Moreover, the recycling of the oxoammonium salt succeeded to convert another proportion of the substrate. These findings offer new insights and methods for the oxidative conversion of cyclohexylamine.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"6 3","pages":"Pages 365-371"},"PeriodicalIF":9.1,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144116668","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01Epub Date: 2025-01-10DOI: 10.1016/j.gce.2025.01.003
Yoshiyasu Takefuji
Mohan et al. developed a feed-forward neural network (FFNN) model to predict Kamlet-Taft parameters using quantum chemically derived features, achieving notable predictive accuracy. However, this study raises concerns about conflating prediction accuracy with feature importance accuracy, as high R2 and low root mean square error (RMSE) do not guarantee valid feature importance assessments. The reliance on SHapley Additive exPlanations (SHAP) for feature evaluation is problematic due to model-specific biases that could misrepresent true associations. A broader understanding of data distribution, statistical relationships, and significance testing through p-values is essential to rectify this. This paper advocates for employing robust statistical methods, like Spearman's correlation, to effectively assess genuine associations and mitigate biases in feature importance analysis.
{"title":"Critical evaluation of feature importance assessment in FFNN-based models for predicting Kamlet-Taft parameters","authors":"Yoshiyasu Takefuji","doi":"10.1016/j.gce.2025.01.003","DOIUrl":"10.1016/j.gce.2025.01.003","url":null,"abstract":"<div><div>Mohan et al. developed a feed-forward neural network (FFNN) model to predict Kamlet-Taft parameters using quantum chemically derived features, achieving notable predictive accuracy. However, this study raises concerns about conflating prediction accuracy with feature importance accuracy, as high R<sup>2</sup> and low root mean square error (RMSE) do not guarantee valid feature importance assessments. The reliance on SHapley Additive exPlanations (SHAP) for feature evaluation is problematic due to model-specific biases that could misrepresent true associations. A broader understanding of data distribution, statistical relationships, and significance testing through p-values is essential to rectify this. This paper advocates for employing robust statistical methods, like Spearman's correlation, to effectively assess genuine associations and mitigate biases in feature importance analysis.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"6 3","pages":"Pages 289-290"},"PeriodicalIF":9.1,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144116105","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01Epub Date: 2024-08-22DOI: 10.1016/j.gce.2024.08.006
Jiaxing Wu , Jiajie Yu , Fan Fan , Runhua Li , Mengxiang Wang , Gang Li , Yuting Wang , Yongpeng Cui , Daoqing Liu , Yajun Wang , Wenqing Yao
Producing hydrogen peroxide (H2O2) through visible-light-driven photocatalytic oxygen reduction in pure water is crucial for sustainable ecological applications but poses significant challenges. It include the rapid recombination of electron-hole pairs and a scarcity of effective catalytic sites, which traditionally limit the process efficiency. To address these issues, we have developed a novel catalyst, designated as KCNOH, which consists of a three-dimensional (3D) porous g-C3N4 framework doped with potassium (K+) and modified with surface hydroxyl groups (–OH). This design significantly enhances H2O2 yield, achieving 91.36 μmol g−1 h−1 (cut 420 nm)—a yield approximately 36 times higher than conventional bulk g-C3N4 (2.57 μmol g−1 h−1). The introduction of a 3D porous structure provides an abundance of active-sites. The dual-dipole mechanism, facilitated by K+ ions and hydroxyl groups, plays a pivotal role by efficiently transporting photogenerated electrons and consuming holes, respectively. Through density functional theory (DFT) calculations, the changes in the band structure of the catalyst caused by the doping of K+ and the grafting of –OH were elucidated. In addition, the transition state affinity of oxygen induced by the –OH was also studied to reveal the synergistic catalytic mechanism. This mechanism markedly reduces carrier recombination and accelerates charge migration, underscoring its importance in catalyst design. Our findings not only improve the understanding of charge dynamics but also open novel perspectives for the design of highly-efficient composite materials, which is crucial for energy and environmental applications.
{"title":"Constructing potassium and hydroxyl co-doped dual-dipole structures on highly active 3D g-C3N4 surfaces for highly boosting photocatalytic hydrogen peroxide production efficiency in pure water","authors":"Jiaxing Wu , Jiajie Yu , Fan Fan , Runhua Li , Mengxiang Wang , Gang Li , Yuting Wang , Yongpeng Cui , Daoqing Liu , Yajun Wang , Wenqing Yao","doi":"10.1016/j.gce.2024.08.006","DOIUrl":"10.1016/j.gce.2024.08.006","url":null,"abstract":"<div><div>Producing hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) through visible-light-driven photocatalytic oxygen reduction in pure water is crucial for sustainable ecological applications but poses significant challenges. It include the rapid recombination of electron-hole pairs and a scarcity of effective catalytic sites, which traditionally limit the process efficiency. To address these issues, we have developed a novel catalyst, designated as KCNOH, which consists of a three-dimensional (3D) porous g-C<sub>3</sub>N<sub>4</sub> framework doped with potassium (K<sup>+</sup>) and modified with surface hydroxyl groups (–OH). This design significantly enhances H<sub>2</sub>O<sub>2</sub> yield, achieving 91.36 μmol g<sup>−1</sup> h<sup>−1</sup> (cut 420 nm)—a yield approximately 36 times higher than conventional bulk g-C<sub>3</sub>N<sub>4</sub> (2.57 μmol g<sup>−1</sup> h<sup>−1</sup>). The introduction of a 3D porous structure provides an abundance of active-sites. The dual-dipole mechanism, facilitated by K<sup>+</sup> ions and hydroxyl groups, plays a pivotal role by efficiently transporting photogenerated electrons and consuming holes, respectively. Through density functional theory (DFT) calculations, the changes in the band structure of the catalyst caused by the doping of K<sup>+</sup> and the grafting of –OH were elucidated. In addition, the transition state affinity of oxygen induced by the –OH was also studied to reveal the synergistic catalytic mechanism. This mechanism markedly reduces carrier recombination and accelerates charge migration, underscoring its importance in catalyst design. Our findings not only improve the understanding of charge dynamics but also open novel perspectives for the design of highly-efficient composite materials, which is crucial for energy and environmental applications.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"6 3","pages":"Pages 388-397"},"PeriodicalIF":9.1,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144116103","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01Epub Date: 2024-03-18DOI: 10.1016/j.gce.2024.03.003
Wei Zhao , Shahid Zaman , Shuhan Kong , Mengqi Liu , Jiexin Zou , Zhen Zhang , Hui Ning , Feng Peng , Yunfei Li , Min Wang , Mingbo Wu
Proton exchange membrane fuel cells (PEMFCs) are efficient and zero emission energy conversion technology with promising application prospects towards carbon neutrality. The PEMFC's performance is largely affected by the poor water management, which is a substantial concern for long term durability. Herein, we overview the water management problems in PEMFCs, such as flooding and dehydration of membrane electrode assembly and analyze the causes and their impacts on the device performance. Major problems such as flooding impedes the gas transport and electrode reactions, while dehydration increases the membrane resistance and hinders proton transport. We have thoroughly overviewed several electrochemical and physicochemical diagnostic techniques for water management in PEMFCs. Additionally, material development and optimization approaches for the flow field structural design are explored in order to improve mass transport and wetting characteristics for optimized water management. Therefore, it is anticipated that this review will provide insights into the effective operation of PEMFCs as well as practical guidance for resolving water management issues in PEMFCs and associated technologies, like PEM water and CO2 electrolyzers.
{"title":"Optimization strategies and diagnostic techniques for water management in proton exchange membrane fuel cells","authors":"Wei Zhao , Shahid Zaman , Shuhan Kong , Mengqi Liu , Jiexin Zou , Zhen Zhang , Hui Ning , Feng Peng , Yunfei Li , Min Wang , Mingbo Wu","doi":"10.1016/j.gce.2024.03.003","DOIUrl":"10.1016/j.gce.2024.03.003","url":null,"abstract":"<div><div>Proton exchange membrane fuel cells (PEMFCs) are efficient and zero emission energy conversion technology with promising application prospects towards carbon neutrality. The PEMFC's performance is largely affected by the poor water management, which is a substantial concern for long term durability. Herein, we overview the water management problems in PEMFCs, such as flooding and dehydration of membrane electrode assembly and analyze the causes and their impacts on the device performance. Major problems such as flooding impedes the gas transport and electrode reactions, while dehydration increases the membrane resistance and hinders proton transport. We have thoroughly overviewed several electrochemical and physicochemical diagnostic techniques for water management in PEMFCs. Additionally, material development and optimization approaches for the flow field structural design are explored in order to improve mass transport and wetting characteristics for optimized water management. Therefore, it is anticipated that this review will provide insights into the effective operation of PEMFCs as well as practical guidance for resolving water management issues in PEMFCs and associated technologies, like PEM water and CO<sub>2</sub> electrolyzers.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"6 3","pages":"Pages 291-304"},"PeriodicalIF":9.1,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140272479","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01Epub Date: 2025-05-23DOI: 10.1016/S2666-9528(25)00023-8
{"title":"OFC: Outside Front Cover","authors":"","doi":"10.1016/S2666-9528(25)00023-8","DOIUrl":"10.1016/S2666-9528(25)00023-8","url":null,"abstract":"","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"6 3","pages":"Page OFC"},"PeriodicalIF":9.1,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144116104","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
For discovering uncharted chemical space of ionic liquids (ILs) for CO2 dissolution, a reliable generative framework combining re-balanced variational autoencoder (VAE), artificial neural network (ANN), and particle swarm optimization (PSO) is developed based on a comprehensive experimental solubility database from literature. The re-balanced VAE transforms the chemical space of ILs into continuous latent space, which is demonstrated by t-distributed stochastic neighbor embedding (t-SNE) visualization and sampled ions of the latent space. ANN is connected with the re-balanced VAE to predict the CO2 solubility and the resultant VAE-ANN model achieves a low mean absolute error (MAE) of 0.022 on the test set. Lastly, the PSO algorithm is employed to search the latent space for optimal IL structures with the highest predicted solubility. A total of 5120 ILs are generated and optimized through 10 parallel runs of PSO. Their CO2 solubilities are predicted and compared to those of the 3735 ILs combined with the already-known cations and anions in the CO2 solubility database under 298.15 K and 100 kPa. The results demonstrate a notably larger distribution of higher CO2 solubility in optimized ILs after PSO, which effectively points out the significance and directions for exploring the wide IL chemical space.
{"title":"Exploring the chemical space of ionic liquids for CO2 dissolution through generative machine learning models","authors":"Xiuxian Chen, Guzhong Chen, Kunchi Xie, Jie Cheng, Jiahui Chen, Zhen Song, Zhiwen Qi","doi":"10.1016/j.gce.2024.06.005","DOIUrl":"10.1016/j.gce.2024.06.005","url":null,"abstract":"<div><div>For discovering uncharted chemical space of ionic liquids (ILs) for CO<sub>2</sub> dissolution, a reliable generative framework combining re-balanced variational autoencoder (VAE), artificial neural network (ANN), and particle swarm optimization (PSO) is developed based on a comprehensive experimental solubility database from literature. The re-balanced VAE transforms the chemical space of ILs into continuous latent space, which is demonstrated by t-distributed stochastic neighbor embedding (t-SNE) visualization and sampled ions of the latent space. ANN is connected with the re-balanced VAE to predict the CO<sub>2</sub> solubility and the resultant VAE-ANN model achieves a low mean absolute error (MAE) of 0.022 on the test set. Lastly, the PSO algorithm is employed to search the latent space for optimal IL structures with the highest predicted solubility. A total of 5120 ILs are generated and optimized through 10 parallel runs of PSO. Their CO<sub>2</sub> solubilities are predicted and compared to those of the 3735 ILs combined with the already-known cations and anions in the CO<sub>2</sub> solubility database under 298.15 K and 100 kPa. The results demonstrate a notably larger distribution of higher CO<sub>2</sub> solubility in optimized ILs after PSO, which effectively points out the significance and directions for exploring the wide IL chemical space.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"6 3","pages":"Pages 335-343"},"PeriodicalIF":9.1,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144116667","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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