Pub Date : 2024-10-15DOI: 10.1016/j.gce.2024.10.003
Gilles Van Eygen , Catherine Echezuria , Anita Buekenhoudt , João A.P. Coutinho , Bart Van der Bruggen , Patricia Luis
Aromatic amines are crucial in pharmaceuticals, but their synthesis is challenging due to unfavorable reaction equilibria and the use of costly, environmentally unfriendly methods. This study presents a membrane extraction (ME) process for in situ product removal (ISPR) of aromatic amines. Using a supported liquid membrane (SLM), -methylbenzylamine (MBA) and 1-methyl-3-phenylpropylamine (MPPA) were separated from isopropyl amine (IPA). Conductor-like Screening Model for Real Solvents (COSMO-RS) was employed to screen over 200 organic mixtures, identifying twelve mixtures based on trioctylphosphine oxide (TOPO), lidocaine, and menthol as solvent candidates, due to their hydrophobicity. These mixtures were analysed for critical solvent properties including density, viscosity, hydrophobicity, and H-bonding interactions. ME tests showed TOPO-thymol had the highest solvent residual and selectivity. Moreover, TOPO-thymol demonstrated solute fluxes of 9.0±3.0 g/(m2 h) for MBA, 16.5±5.4 g/(m2 h) for MPPA, and 0.7±0.3 g/(m2 h) for IPA, with selectivity values of 12.4±0.8 for MBA/IPA and 22.8±1.4 for MPPA/IPA. Compared to undecane, which had lower selectivity values of 6.9±0.8 for MBA/IPA and 10.1±1.3 for MPPA/IPA, TOPO-thymol showed superior selectivity, indicating its promise as an extractant for ME applications.
{"title":"COSMO-RS screening of organic mixtures for membrane extraction of aromatic amines: TOPO-based mixtures as promising solvents","authors":"Gilles Van Eygen , Catherine Echezuria , Anita Buekenhoudt , João A.P. Coutinho , Bart Van der Bruggen , Patricia Luis","doi":"10.1016/j.gce.2024.10.003","DOIUrl":"10.1016/j.gce.2024.10.003","url":null,"abstract":"<div><div>Aromatic amines are crucial in pharmaceuticals, but their synthesis is challenging due to unfavorable reaction equilibria and the use of costly, environmentally unfriendly methods. This study presents a membrane extraction (ME) process for <em>in situ</em> product removal (ISPR) of aromatic amines. Using a supported liquid membrane (SLM), <span><math><mrow><mi>α</mi></mrow></math></span>-methylbenzylamine (MBA) and 1-methyl-3-phenylpropylamine (MPPA) were separated from isopropyl amine (IPA). Conductor-like Screening Model for Real Solvents (COSMO-RS) was employed to screen over 200 organic mixtures, identifying twelve mixtures based on trioctylphosphine oxide (TOPO), lidocaine, and menthol as solvent candidates, due to their hydrophobicity. These mixtures were analysed for critical solvent properties including density, viscosity, hydrophobicity, and H-bonding interactions. ME tests showed TOPO-thymol had the highest solvent residual and selectivity. Moreover, TOPO-thymol demonstrated solute fluxes of 9.0±3.0 g/(m<sup>2</sup> h) for MBA, 16.5±5.4 g/(m<sup>2</sup> h) for MPPA, and 0.7±0.3 g/(m<sup>2</sup> h) for IPA, with selectivity values of 12.4±0.8 for MBA/IPA and 22.8±1.4 for MPPA/IPA. Compared to undecane, which had lower selectivity values of 6.9±0.8 for MBA/IPA and 10.1±1.3 for MPPA/IPA, TOPO-thymol showed superior selectivity, indicating its promise as an extractant for ME applications.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"6 2","pages":"Pages 263-274"},"PeriodicalIF":9.1,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143594165","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 : 2024-10-09DOI: 10.1016/j.gce.2024.10.002
Atul A. Pawar , S. Anuradha Jabasingh , Shimelis Kebede Kassahun , Hern Kim
The direct conversion of carbon dioxide (CO2) and propylene oxide (PO) into propylene carbonate (PC) offers a green way to utilize anthropogenic CO2. However, this reaction is limited by low conversion of PO and harsh reaction conditions. In this study, we solve this problem using ionic liquids (ILs)/metal oxide composites (ILs@MAO). The catalytic activity of MAO-500 (500 = annealing temperature) is poor evidenced by its low conversion of PO (24.94%). However, ILs@MAO-500 has a high conversion of PO (97.54%) under similar reaction conditions (2 h at 1.5 MPa CO2 pressure, 90 °C, and 0.85 g catalyst). The ILs consist of imidazolium cation with weak coordinated [NTf2]– anion leading to outward movement of anion resulting in the formation of “heterodinuclear complex”. This complex generates an amorphous-crystalline intermediate with balanced acid-base sites that activate PO and stabilize the catalytic intermediate. In large part, the high PO conversion is theorized to be primarily due to the abundant reactive sites in the ILs that are covalently immobilized on the MAO-500 carrier. Furthermore, even after multiple recycling, ILs@MAO-500 remains stable and exhibits high yield and selectivity. The proposed solvent-free catalytic system is mild, kinetically fast, and naturally safe for coupling CO2 and PO into PC synthesis.
{"title":"Incorporation of Mg/Al metal oxide into ionic liquids for CO2 capture and conversion into cyclic carbonate under solvent-free conditions: effect of coordination ability, recyclability, and catalytic study","authors":"Atul A. Pawar , S. Anuradha Jabasingh , Shimelis Kebede Kassahun , Hern Kim","doi":"10.1016/j.gce.2024.10.002","DOIUrl":"10.1016/j.gce.2024.10.002","url":null,"abstract":"<div><div>The direct conversion of carbon dioxide (CO<sub>2</sub>) and propylene oxide (PO) into propylene carbonate (PC) offers a green way to utilize anthropogenic CO<sub>2</sub>. However, this reaction is limited by low conversion of PO and harsh reaction conditions. In this study, we solve this problem using ionic liquids (ILs)/metal oxide composites (ILs@MAO). The catalytic activity of MAO-500 (500 = annealing temperature) is poor evidenced by its low conversion of PO (24.94%). However, ILs@MAO-500 has a high conversion of PO (97.54%) under similar reaction conditions (2 h at 1.5 MPa CO<sub>2</sub> pressure, 90 °C, and 0.85 g catalyst). The ILs consist of imidazolium cation with weak coordinated [NTf<sub>2</sub>]<sup>–</sup> anion leading to outward movement of anion resulting in the formation of “heterodinuclear complex”. This complex generates an amorphous-crystalline intermediate with balanced acid-base sites that activate PO and stabilize the catalytic intermediate. In large part, the high PO conversion is theorized to be primarily due to the abundant reactive sites in the ILs that are covalently immobilized on the MAO-500 carrier. Furthermore, even after multiple recycling, ILs@MAO-500 remains stable and exhibits high yield and selectivity. The proposed solvent-free catalytic system is mild, kinetically fast, and naturally safe for coupling CO<sub>2</sub> and PO into PC synthesis.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"7 1","pages":"Pages 121-130"},"PeriodicalIF":7.6,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145420214","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 : 2024-10-05DOI: 10.1016/j.gce.2024.10.001
Balkis Hazmi , Umer Rashid , Bryan R. Moser , Mohd Hafizuddin Ab Ghani , Fahad A. Alharthi , Jeehoon Han , Jiyun Yoo
Heterogeneous acidic Zr-MOF (metal-organic framework) catalyst, UiO-66/SO3H was synthesized for palm fatty acid distillate (PFAD)-methanol esterification. The characterizations for catalyst precursor and active catalyst were carried out using infrared spectroscopy, ammonia-temperature desorption analysis, thermogravimetric analyser, X-ray diffraction, surface textural analyser, and field emission scanning microscopy. The surface area of UiO-66 and UiO-66/SO3H was 714.77 m2/g and 503.02 m2/g, respectively. Meanwhile, the acidity strength shown an increase in values, rising from 3.14 mmol/g to 7.98 mmol/g. Throughout the catalytic screening test under fixed parameters, UiO-66/SO3H produced 72.3% of fatty acid methyl ester (FAME) while 45.9% catalyzed by UiO-66. Then, UiO-66/SO3H was selected for response surface methodology-central composite design (RSM-CCD) optimization. Following 31 experiments, the optimized conditions were determined to be 75 °C, 1.3 h, 4.2 wt% catalyst, and a methanol to PFAD molar ratio of 21:1, resulting in a yield of 98.6% FAME. Reusability tests demonstrated that the catalyst maintained its activity for seven cycles, averaging 72.4% yield but subsequently dropping to 53.8% after the eighth cycle. Environmental sustainability was evaluated using life-cycle assessment (LCA) across seven impact categories: global warming potential, stratospheric ozone depletion, acidification potential, terrestrial ecotoxicity, freshwater ecotoxicity, marine ecotoxicity, and fossil resource scarcity. LCA analysis revealed that the PFAD process had a substantial global warming impact, with the exception of microalgae-based biodiesel. The PFAD process has lower acidification potential than soybean or lignocellulosic biomass. Our advanced biodiesel production method, with minimal methanol and low electricity, is an environmentally friendly alternative.
{"title":"Environmentally sustainable production of biodiesel from low-cost lipid feedstock using a zirconium-based metal-organic framework sulfonated solid catalyst","authors":"Balkis Hazmi , Umer Rashid , Bryan R. Moser , Mohd Hafizuddin Ab Ghani , Fahad A. Alharthi , Jeehoon Han , Jiyun Yoo","doi":"10.1016/j.gce.2024.10.001","DOIUrl":"10.1016/j.gce.2024.10.001","url":null,"abstract":"<div><div>Heterogeneous acidic Zr-MOF (metal-organic framework) catalyst, UiO-66/SO<sub>3</sub>H was synthesized for palm fatty acid distillate (PFAD)-methanol esterification. The characterizations for catalyst precursor and active catalyst were carried out using infrared spectroscopy, ammonia-temperature desorption analysis, thermogravimetric analyser, X-ray diffraction, surface textural analyser, and field emission scanning microscopy. The surface area of UiO-66 and UiO-66/SO<sub>3</sub>H was 714.77 m<sup>2</sup>/g and 503.02 m<sup>2</sup>/g, respectively. Meanwhile, the acidity strength shown an increase in values, rising from 3.14 mmol/g to 7.98 mmol/g. Throughout the catalytic screening test under fixed parameters, UiO-66/SO<sub>3</sub>H produced 72.3% of fatty acid methyl ester (FAME) while 45.9% catalyzed by UiO-66. Then, UiO-66/SO<sub>3</sub>H was selected for response surface methodology-central composite design (RSM-CCD) optimization. Following 31 experiments, the optimized conditions were determined to be 75 °C, 1.3 h, 4.2 wt% catalyst, and a methanol to PFAD molar ratio of 21:1, resulting in a yield of 98.6% FAME. Reusability tests demonstrated that the catalyst maintained its activity for seven cycles, averaging 72.4% yield but subsequently dropping to 53.8% after the eighth cycle. Environmental sustainability was evaluated using life-cycle assessment (LCA) across seven impact categories: global warming potential, stratospheric ozone depletion, acidification potential, terrestrial ecotoxicity, freshwater ecotoxicity, marine ecotoxicity, and fossil resource scarcity. LCA analysis revealed that the PFAD process had a substantial global warming impact, with the exception of microalgae-based biodiesel. The PFAD process has lower acidification potential than soybean or lignocellulosic biomass. Our advanced biodiesel production method, with minimal methanol and low electricity, is an environmentally friendly alternative.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"7 1","pages":"Pages 94-108"},"PeriodicalIF":7.6,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145420209","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 : 2024-10-05DOI: 10.1016/j.gce.2024.09.011
Yang Liu , Yuxiang Chen , Chuanlei Liu , Yupeng Cui , Qiyue Zhao , Guanchu Guo , Hao Jiang , Qiumin Wu , Haiyang Wen , Fahai Cao , Benxian Shen , Hui Sun
Machine learning (ML) algorithms are playing increasingly important roles in exploring solvents for wide industrial applications. However, most ML strategies for solvent screening neglect the contributions of intermolecular interactions among solvent components, resulting in reduced prediction accuracy for the solubilities of solvent mixtures. In this study, we propose an efficient method combining feature-based transfer learning and a hybrid Henry's law constant (HLC) calculation method to assist the exploration of promising solvent mixtures to remove organic sulfides. The incorporation of predicted HLC values from established models as features significantly enhances the prediction accuracy for various organic sulfides. In the case of 2-propanethiol, the prediction shows a R2test of 0.91, RMSE of 0.0166, and MAE of 0.0118. The hybrid HLC calculation method, which incorporates non-ideal interactions between two solvent components, outperforms both the conductor-like screening models for real solvents (COSMO-RS) and ideal solution methods in predicting experimental HLC values. The present method successfully predicts a hybrid solvent for methanethiol (MeSH) removal. Both static and dynamic absorption experiments confirm that this designed solvent mixture has the lowest HLC of 370.48 kPa and the highest removal rate of 80.38% for MeSH.
{"title":"Prediction of organic sulfur solubility in mixed solvent using feature-based transfer learning and a hybrid Henry's law constant calculation method","authors":"Yang Liu , Yuxiang Chen , Chuanlei Liu , Yupeng Cui , Qiyue Zhao , Guanchu Guo , Hao Jiang , Qiumin Wu , Haiyang Wen , Fahai Cao , Benxian Shen , Hui Sun","doi":"10.1016/j.gce.2024.09.011","DOIUrl":"10.1016/j.gce.2024.09.011","url":null,"abstract":"<div><div>Machine learning (ML) algorithms are playing increasingly important roles in exploring solvents for wide industrial applications. However, most ML strategies for solvent screening neglect the contributions of intermolecular interactions among solvent components, resulting in reduced prediction accuracy for the solubilities of solvent mixtures. In this study, we propose an efficient method combining feature-based transfer learning and a hybrid Henry's law constant (HLC) calculation method to assist the exploration of promising solvent mixtures to remove organic sulfides. The incorporation of predicted HLC values from established models as features significantly enhances the prediction accuracy for various organic sulfides. In the case of 2-propanethiol, the prediction shows a R<sup>2</sup><sub>test</sub> of 0.91, RMSE of 0.0166, and MAE of 0.0118. The hybrid HLC calculation method, which incorporates non-ideal interactions between two solvent components, outperforms both the conductor-like screening models for real solvents (COSMO-RS) and ideal solution methods in predicting experimental HLC values. The present method successfully predicts a hybrid solvent for methanethiol (MeSH) removal. Both static and dynamic absorption experiments confirm that this designed solvent mixture has the lowest HLC of 370.48 kPa and the highest removal rate of 80.38% for MeSH.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"7 1","pages":"Pages 109-120"},"PeriodicalIF":7.6,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145420207","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 : 2024-09-30DOI: 10.1016/j.gce.2024.09.012
Junfa Yuan , Jinshu Huang , Joseph VL. Ruatpuia , Jiasheng Chen , Huan Wang , Samuel Lalthazuala Rokhum , Hu Li
Deep eutectic solvent (DES) pretreatment is attractive for the delignification of lignocellulosic biomass, while unable to circumvent the trenchant demand for the higher-temperature operating conditions. Herein, an electro-assisted DES (choline chloride/ethylene glycol = 1:2) strategy was developed for wheat straw pretreatment at room temperature. The rate of lignin removal, hemicellulose removal, cellulose recovery, and cellulose saccharification reached 68.1%, 60.8%, 95.1%, and 82.5%, respectively, which were comparable or superior to the reported efficiency of traditional DES pretreatment methods. The destruction of lignin by electricity and in-situ dissolution of released lignin components with DES enabled effectively the separation of the full components. Notably, the evolution rate of hydrogen in-situ produced during electro-driven DES pretreatment of wheat straw was 50 μmol cm−2 h−1, and 4.6 g/100 g lipids could be obtained with Trichosporon cutaneum grown on the fractionated cellulose and hemicellulose components. The electro-assisted DES process offers a potential platform for lignocellulosic biomass fractionation at ambient conditions. According to the life cycle cost analysis (LCCA), the estimated cost of producing hydrogen from 100 g of wheat straw is only $37.24, demonstrating its potential for commercial viability.
{"title":"Electro-driven deep eutectic solvent pretreatment of wheat straw with enhancive component fractionation and hydrogen evolution at room temperature","authors":"Junfa Yuan , Jinshu Huang , Joseph VL. Ruatpuia , Jiasheng Chen , Huan Wang , Samuel Lalthazuala Rokhum , Hu Li","doi":"10.1016/j.gce.2024.09.012","DOIUrl":"10.1016/j.gce.2024.09.012","url":null,"abstract":"<div><div>Deep eutectic solvent (DES) pretreatment is attractive for the delignification of lignocellulosic biomass, while unable to circumvent the trenchant demand for the higher-temperature operating conditions. Herein, an electro-assisted DES (choline chloride/ethylene glycol = 1:2) strategy was developed for wheat straw pretreatment at room temperature. The rate of lignin removal, hemicellulose removal, cellulose recovery, and cellulose saccharification reached 68.1%, 60.8%, 95.1%, and 82.5%, respectively, which were comparable or superior to the reported efficiency of traditional DES pretreatment methods. The destruction of lignin by electricity and <em>in-situ</em> dissolution of released lignin components with DES enabled effectively the separation of the full components. Notably, the evolution rate of hydrogen <em>in</em><em>-</em><em>situ</em> produced during electro-driven DES pretreatment of wheat straw was 50 μmol cm<sup>−2</sup> h<sup>−1</sup>, and 4.6 g/100 g lipids could be obtained with <em>Trichosporon cutaneum</em> grown on the fractionated cellulose and hemicellulose components. The electro-assisted DES process offers a potential platform for lignocellulosic biomass fractionation at ambient conditions. According to the life cycle cost analysis (LCCA), the estimated cost of producing hydrogen from 100 g of wheat straw is only $37.24, demonstrating its potential for commercial viability.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"7 1","pages":"Pages 83-93"},"PeriodicalIF":7.6,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145420210","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 : 2024-09-27DOI: 10.1016/j.gce.2024.09.010
Chengtao Yue , Xu Zhang , Hong Li , Chuanlei Luo , Fuwei Li
The increasingly environmental pollution have drawn global attentions to the development of new techniques that can effectively deal with the pollutants. With the unique set of electronic properties and structural diversities, N-heterocyclic carbenes (NHCs) and related materials are emerging as potential adsorbing materials for adsorptive decontamination of various pollutant-containing mediums. Recent investigations have revealed the feasibility of molecular and heterogeneous NHCs for adsorptive separation of harmful gases including CO2, CO, NOx, SO2, etc. Rather than simple gas trapping, NHCs functions as effective catalytic centers that activating and transforming the captured gas molecules. Besides, heterogeneous NHCs and their complexes have been applied to adsorptive removal of various organic pollutants and heavy metal ions from water solution with high efficiencies. These advancements have illustrated the significant potential of NHCs and their related materials in environmental decontamination. Instead of the well-known catalytic applications of NHCs in organic transformations, this review aims to offer an overview of the emerging applications of NHCs in the field of environmental decontamination and provide a comprehensive understanding of the mechanisms behind the N-heterocyclic carbene material-mediated environmental decontamination processes. With this in mind, the structure, synthesis, application, and performance of NHCs and related materials in environmental processes including gas separation and wastewater treatment are summarized, and the structure-activity relationship is discussed. Besides, the current challenge and future development of NHC-mediated environmental treatments are proposed. This review is expected to serve as a preliminary database for the environmental applications of NHC and related materials and offer deep insights into the rational design of novel NHC-based environmental materials for greener and efficient environmental processes.
{"title":"Emerging applications of N-heterocyclic carbenes and related materials in environmental decontamination","authors":"Chengtao Yue , Xu Zhang , Hong Li , Chuanlei Luo , Fuwei Li","doi":"10.1016/j.gce.2024.09.010","DOIUrl":"10.1016/j.gce.2024.09.010","url":null,"abstract":"<div><div>The increasingly environmental pollution have drawn global attentions to the development of new techniques that can effectively deal with the pollutants. With the unique set of electronic properties and structural diversities, N-heterocyclic carbenes (NHCs) and related materials are emerging as potential adsorbing materials for adsorptive decontamination of various pollutant-containing mediums. Recent investigations have revealed the feasibility of molecular and heterogeneous NHCs for adsorptive separation of harmful gases including CO<sub>2</sub>, CO, NO<sub><em>x</em></sub>, SO<sub>2</sub>, etc. Rather than simple gas trapping, NHCs functions as effective catalytic centers that activating and transforming the captured gas molecules. Besides, heterogeneous NHCs and their complexes have been applied to adsorptive removal of various organic pollutants and heavy metal ions from water solution with high efficiencies. These advancements have illustrated the significant potential of NHCs and their related materials in environmental decontamination. Instead of the well-known catalytic applications of NHCs in organic transformations, this review aims to offer an overview of the emerging applications of NHCs in the field of environmental decontamination and provide a comprehensive understanding of the mechanisms behind the N-heterocyclic carbene material-mediated environmental decontamination processes. With this in mind, the structure, synthesis, application, and performance of NHCs and related materials in environmental processes including gas separation and wastewater treatment are summarized, and the structure-activity relationship is discussed. Besides, the current challenge and future development of NHC-mediated environmental treatments are proposed. This review is expected to serve as a preliminary database for the environmental applications of NHC and related materials and offer deep insights into the rational design of novel NHC-based environmental materials for greener and efficient environmental processes.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"7 1","pages":"Pages 1-16"},"PeriodicalIF":7.6,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145420217","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 : 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":"2024-09-26","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 : 2024-09-26DOI: 10.1016/j.gce.2024.09.008
Xi Liu , Fangqian Wang , Yongrong Li , Xuebing Zhao
A new coupled electrolysis system has been developed by combining pretreatment of lignocellulosic biomass (corn stover) in alkaline anolyte for increasing cellulose digestibility with electrochemical reduction of CO2 on the cathode to produce formic acid. Electrodeposition of Sn on calcinated copper foam results in preparation of an efficient cathode, ED-Sn@CuOx, achieving 83.2% Faradaic efficiency of formate formation with a current density of 69.2 mA cm-2 in an H-type electrolysis cell. The ferricyanide/ferrocyanide redox couple plays an efficient electron mediator to improve the rate of electron transfer. Oxygen evolution reaction can be significantly suppressed, increasing the production rate of formate. Corn stover can be simultaneously pretreated by delignification in alkaline anolyte. Under the relatively optimal condition, the pretreated substrates obtained 96.6% glucose yield and 83.4% xylose yield. By inputting 1 kWh of electricity, the coupled system can obtain 0.27 kg formate with simultaneously pretreating 31.1 kg corn stover, resulting in the production of 14.2 kg fermentable sugars by subsequent enzymatic hydrolysis. Meanwhile, alkaline delignification in the anolyte also plays an important role in the increase of the pretreatment efficiency.
将木质纤维素生物质（玉米秸秆）在碱性阳极液中预处理以提高纤维素的消化率与阴极上电化学还原CO2生成甲酸相结合，建立了一种新的耦合电解系统。在h型电解池中，将Sn电沉积在煅烧的泡沫铜上，制备了高效阴极ED-Sn@CuOx，在电流密度为69.2 mA cm-2的情况下，形成甲酸盐的法拉第效率达到83.2%。铁氰化物/亚铁氰化物氧化还原偶对是提高电子转移速率的有效电子介质。可以明显抑制析氧反应，提高甲酸酯的产率。玉米秸秆可在碱性阳极液中同时进行脱木质素预处理。在相对最佳的条件下，预处理后的底物葡萄糖产率为96.6%，木糖产率为83.4%。通过输入1 kWh的电力，耦合系统可在预处理31.1 kg玉米秸秆的同时获得0.27 kg甲酸盐，并通过后续酶解生产14.2 kg可发酵糖。同时，阳极液中的碱性脱木质素作用对提高预处理效率也起着重要作用。
{"title":"Coupling pretreatment of lignocellulosic biomass for enzymatic hydrolysis with electrochemical reduction of CO2 for production of formic acid","authors":"Xi Liu , Fangqian Wang , Yongrong Li , Xuebing Zhao","doi":"10.1016/j.gce.2024.09.008","DOIUrl":"10.1016/j.gce.2024.09.008","url":null,"abstract":"<div><div>A new coupled electrolysis system has been developed by combining pretreatment of lignocellulosic biomass (corn stover) in alkaline anolyte for increasing cellulose digestibility with electrochemical reduction of CO<sub>2</sub> on the cathode to produce formic acid. Electrodeposition of Sn on calcinated copper foam results in preparation of an efficient cathode, ED-Sn@CuO<sub><em>x</em></sub>, achieving 83.2% Faradaic efficiency of formate formation with a current density of 69.2 mA cm<sup>-</sup><sup>2</sup> in an H-type electrolysis cell. The ferricyanide/ferrocyanide redox couple plays an efficient electron mediator to improve the rate of electron transfer. Oxygen evolution reaction can be significantly suppressed, increasing the production rate of formate. Corn stover can be simultaneously pretreated by delignification in alkaline anolyte. Under the relatively optimal condition, the pretreated substrates obtained 96.6% glucose yield and 83.4% xylose yield. By inputting 1 kWh of electricity, the coupled system can obtain 0.27 kg formate with simultaneously pretreating 31.1 kg corn stover, resulting in the production of 14.2 kg fermentable sugars by subsequent enzymatic hydrolysis. Meanwhile, alkaline delignification in the anolyte also plays an important role in the increase of the pretreatment efficiency.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"7 1","pages":"Pages 70-82"},"PeriodicalIF":7.6,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145420208","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 : 2024-09-25DOI: 10.1016/j.gce.2024.09.007
Yingchun Niu , Qingtan Gao , Runfa Zhao , Ziyu Liu , Ruichen Zhou , Shengwei Yuan , Jinfeng Yi , Wei Qiu , Chunming Xu , Quan Xu
The electrolyte in the flow battery is the carrier of energy storage, however, there are few studies on electrolyte for iron-chromium redox flow batteries (ICRFB). The low utilization rate and rapid capacity decay of ICRFB electrolyte have always been a challenging problem. Herein, the effect of Fe/Cr molar ratio, and concentration of HCl on the performance of ICRFBs at high current density (140 mA cm−2) are investigated. The average energy efficiency of the optimal electrolyte (1.25 M FeCl2, 1.50 M CrCl3, 3.0 M HCl) increases by 5.99% in the first 20 cycles, and the discharge capacity increases by 15.72% in the first cycle compared to the original commercial electrolyte (1.0 M FeCl2, 1.0 M CrCl3, 3.0 M HCl). This electrolyte also shows a longer cycle life. In addition, the COMSOL simulation on the concentration change of electrolyte in ICRFB is proposed, the effect of physical properties on the electrolyte is further explained. Through the simulation and analysis of this complex system, researchers can better understand the performance of flow battery systems. It is important to consider various challenges and constraints that might be encountered in practical applications. This work effectively saves the cost of ICRFB and further provides data support for their engineering applications.
液流电池中的电解液是储能的载体，但对铁铬氧化还原液流电池（ICRFB）电解液的研究较少。ICRFB电解液的利用率低、容量衰减快一直是一个具有挑战性的问题。本文研究了Fe/Cr摩尔比和HCl浓度对高电流密度（140 mA cm−2）下icrfb性能的影响。优化后的电解液（1.25 M FeCl2、1.50 M CrCl3、3.0 M HCl）在前20次循环中的平均能效比原商用电解液（1.0 M FeCl2、1.0 M CrCl3、3.0 M HCl）提高了5.99%，第一次循环的放电容量提高了15.72%。这种电解质也显示出更长的循环寿命。此外，提出了COMSOL模拟ICRFB中电解液浓度变化的方法，进一步解释了物理性质对电解液的影响。通过对这一复杂系统的仿真和分析，研究人员可以更好地了解液流电池系统的性能。考虑在实际应用中可能遇到的各种挑战和限制是很重要的。这项工作有效地节省了ICRFB的成本，并进一步为其工程应用提供了数据支持。
{"title":"A high current density and long cycle life iron-chromium redox flow battery electrolyte","authors":"Yingchun Niu , Qingtan Gao , Runfa Zhao , Ziyu Liu , Ruichen Zhou , Shengwei Yuan , Jinfeng Yi , Wei Qiu , Chunming Xu , Quan Xu","doi":"10.1016/j.gce.2024.09.007","DOIUrl":"10.1016/j.gce.2024.09.007","url":null,"abstract":"<div><div>The electrolyte in the flow battery is the carrier of energy storage, however, there are few studies on electrolyte for iron-chromium redox flow batteries (ICRFB). The low utilization rate and rapid capacity decay of ICRFB electrolyte have always been a challenging problem. Herein, the effect of Fe/Cr molar ratio, and concentration of HCl on the performance of ICRFBs at high current density (140 mA cm<sup>−2</sup>) are investigated. The average energy efficiency of the optimal electrolyte (1.25 M FeCl<sub>2</sub>, 1.50 M CrCl<sub>3</sub>, 3.0 M HCl) increases by 5.99% in the first 20 cycles, and the discharge capacity increases by 15.72% in the first cycle compared to the original commercial electrolyte (1.0 M FeCl<sub>2</sub>, 1.0 M CrCl<sub>3</sub>, 3.0 M HCl). This electrolyte also shows a longer cycle life. In addition, the COMSOL simulation on the concentration change of electrolyte in ICRFB is proposed, the effect of physical properties on the electrolyte is further explained. Through the simulation and analysis of this complex system, researchers can better understand the performance of flow battery systems. It is important to consider various challenges and constraints that might be encountered in practical applications. This work effectively saves the cost of ICRFB and further provides data support for their engineering applications.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"7 1","pages":"Pages 61-69"},"PeriodicalIF":7.6,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145420211","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}
Global warming caused primarily by excessive emissions of CO2 has attracted worldwide attention. Herein, three 2-hydroxypyridium ionic liquids (ILs) based task-specific deep eutectic solvents (DESs) were synthesized to absorb CO2 and physical properties including density, viscosity, and melting points were measured to explore the effect on CO2 absorption. The CO2 absorption capacities of the ILs-based task-specific DESs were investigated at different pressures and temperatures, which showed that the maximum absorption capacity of the DES was up to 1.48 molCO2·molDES−1 or 0.233 gCO2·gDES−1 at the atmospheric pressure and 25 °C. The plausible absorption mechanism was also proposed by a combination of 1:1 and 2:1 stoichiometric reactions of CO2 and the IL-based task-specific DES via multiple-site absorption, which was confirmed by 13C and 1H nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR) spectroscopy, quantum chemical calculation, and reaction equilibrium thermodynamic modeling. The thermodynamic properties, including absorption Gibbs free energy, absorption enthalpy, and absorption entropy were rationally deduced and explained. Furthermore, the excellent CO2 absorption capacity and regenerability of multiple-site task-specific DES make it a new environmentally eco-friendly choice for highly efficient CO2 absorption and subsequent CO2 transformation.
{"title":"Multiple-site absorption of CO2 in 2-hydroxypyridium ionic liquids based task-specific deep eutectic solvents","authors":"Xinzi Wu, Jiawei Ruan, Ke Wang, Xiaoyi Zhang, Mingfeng Ma, Lifang Chen, Zhiwen Qi","doi":"10.1016/j.gce.2024.09.005","DOIUrl":"10.1016/j.gce.2024.09.005","url":null,"abstract":"<div><div>Global warming caused primarily by excessive emissions of CO<sub>2</sub> has attracted worldwide attention. Herein, three 2-hydroxypyridium ionic liquids (ILs) based task-specific deep eutectic solvents (DESs) were synthesized to absorb CO<sub>2</sub> and physical properties including density, viscosity, and melting points were measured to explore the effect on CO<sub>2</sub> absorption. The CO<sub>2</sub> absorption capacities of the ILs-based task-specific DESs were investigated at different pressures and temperatures, which showed that the maximum absorption capacity of the DES was up to 1.48 mol<sub>CO2</sub>·mol<sub>DES</sub><sup>−1</sup> or 0.233 g<sub>CO2</sub>·g<sub>DES</sub><sup>−1</sup> at the atmospheric pressure and 25 °C. The plausible absorption mechanism was also proposed by a combination of 1:1 and 2:1 stoichiometric reactions of CO<sub>2</sub> and the IL-based task-specific DES <em>via</em> multiple-site absorption, which was confirmed by <sup>13</sup>C and <sup>1</sup>H nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR) spectroscopy, quantum chemical calculation, and reaction equilibrium thermodynamic modeling. The thermodynamic properties, including absorption Gibbs free energy, absorption enthalpy, and absorption entropy were rationally deduced and explained. Furthermore, the excellent CO<sub>2</sub> absorption capacity and regenerability of multiple-site task-specific DES make it a new environmentally eco-friendly choice for highly efficient CO<sub>2</sub> absorption and subsequent CO<sub>2</sub> transformation.</div></div>","PeriodicalId":66474,"journal":{"name":"Green Chemical Engineering","volume":"7 1","pages":"Pages 38-50"},"PeriodicalIF":7.6,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145420216","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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