Pub Date : 2025-01-21DOI: 10.1021/acssuschemeng.4c09012
Xiaoyun Du, Jun Chang
Ternesite has been proven to have significant competitiveness as an ultralow lime CO2 sequestration binder. It is worthy of industrial production for CO2 emission reduction in the cement industry. MgO is inevitable in natural limestone, which may change ternesite’s sintering and carbonation properties. This study aims to simulate the effect of MgO content on the sintering and carbonation behavior of ternesite. The results show that less than 4% Mg2+ is dissolved in the crystal structure of ternesite by replacing Ca2+ and induces a reduction of cell size. More than 4% MgO will be sintered to form bredigite and merwinite, restraining ternesite content in clinkers. The compressive strength of ternesite clinker compacts is negatively correlated with the MgO doping content. The increase in MgO doping from 0 to 20% resulted in a 68.2% decrease in compressive strength. MgO doping less than or equal to 3% improves the CO2 sequestration capacity of ternesite clinkers by 4.1%; however, more than or equal to 5% will reduce the CO2 sequestration capacity. The analysis of carbonation products showed that MgO reduced the content of aragonite and vaterite and induced the formation of magnesian calcite and monohydrocalcite. The difference in ternesite content, crystal morphology, and carbonation products is the reason for the change in carbonation properties of MgO-doped clinkers.
{"title":"MgO Doping on the Sintering and Carbonation Properties of Ternesite","authors":"Xiaoyun Du, Jun Chang","doi":"10.1021/acssuschemeng.4c09012","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09012","url":null,"abstract":"Ternesite has been proven to have significant competitiveness as an ultralow lime CO<sub>2</sub> sequestration binder. It is worthy of industrial production for CO<sub>2</sub> emission reduction in the cement industry. MgO is inevitable in natural limestone, which may change ternesite’s sintering and carbonation properties. This study aims to simulate the effect of MgO content on the sintering and carbonation behavior of ternesite. The results show that less than 4% Mg<sup>2+</sup> is dissolved in the crystal structure of ternesite by replacing Ca<sup>2+</sup> and induces a reduction of cell size. More than 4% MgO will be sintered to form bredigite and merwinite, restraining ternesite content in clinkers. The compressive strength of ternesite clinker compacts is negatively correlated with the MgO doping content. The increase in MgO doping from 0 to 20% resulted in a 68.2% decrease in compressive strength. MgO doping less than or equal to 3% improves the CO<sub>2</sub> sequestration capacity of ternesite clinkers by 4.1%; however, more than or equal to 5% will reduce the CO<sub>2</sub> sequestration capacity. The analysis of carbonation products showed that MgO reduced the content of aragonite and vaterite and induced the formation of magnesian calcite and monohydrocalcite. The difference in ternesite content, crystal morphology, and carbonation products is the reason for the change in carbonation properties of MgO-doped clinkers.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142991588","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-21DOI: 10.1021/acssuschemeng.4c07235
Triya Mukherjee, S. Venkata Mohan
Succinic acid (SA), an important industrial chemical, is traditionally produced via petrochemicals, generating significant greenhouse gases. Thus, the transition to sustainable biomanufacturing is critical for reducing emissions. However, a major challenge in bio-based SA production at an industrial scale is the generation of acetic acid (AA) as a byproduct, which reduces the SA yield and process efficiency. In this study, we demonstrated the potential of electro-fermentation (EF) as an innovative method for selective SA from Citrobacter amalonaticus (IICTSVMSA1) in a nongenetic approach with glycerol (30 g/L), MgCO3 (10 g/L) and CO2 (0.093 L/100 mL) as feedstocks. By downregulating the pyruvate dehydrogenase (ace) gene (regulating the pyruvate channel) with an electrode assembly and poised potential (−0.6 V), the production of AA was reduced by 30%. This resulted in a higher SA titer (17.4 g/L; 0.58 g/g) compared to our control condition (7.4 g/L; 0.25 g/g). We further performed sustainability analysis and planetary boundaries assessment, which revealed that the petrochemical process for SA production emits 3 times more CO2 (6.9 kg/eq) and has a more environmental impact compared to the biological route (glucose─2.9 kg/eq; glycerol─2.4 kg/eq). Our findings can underscore the potential of EF toward selective SA production, which can be used in the bio-based SA-producing industries where product selectivity and down-streaming are crucial challenges.
{"title":"Bio-Electrocatalytically Regulated Selective Succinic Acid Production by Suppressing Pyruvate Channel Using Glycerol and CO2","authors":"Triya Mukherjee, S. Venkata Mohan","doi":"10.1021/acssuschemeng.4c07235","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07235","url":null,"abstract":"Succinic acid (SA), an important industrial chemical, is traditionally produced via petrochemicals, generating significant greenhouse gases. Thus, the transition to sustainable biomanufacturing is critical for reducing emissions. However, a major challenge in bio-based SA production at an industrial scale is the generation of acetic acid (AA) as a byproduct, which reduces the SA yield and process efficiency. In this study, we demonstrated the potential of electro-fermentation (EF) as an innovative method for selective SA from <i>Citrobacter amalonaticus</i> (IICTSVMSA1) in a nongenetic approach with glycerol (30 g/L), MgCO<sub>3</sub> (10 g/L) and CO<sub>2</sub> (0.093 L/100 mL) as feedstocks. By downregulating the pyruvate dehydrogenase (<i>ace</i>) gene (regulating the pyruvate channel) with an electrode assembly and poised potential (−0.6 V), the production of AA was reduced by 30%. This resulted in a higher SA titer (17.4 g/L; 0.58 g/g) compared to our control condition (7.4 g/L; 0.25 g/g). We further performed sustainability analysis and planetary boundaries assessment, which revealed that the petrochemical process for SA production emits 3 times more CO<sub>2</sub> (6.9 kg/eq) and has a more environmental impact compared to the biological route (glucose─2.9 kg/eq; glycerol─2.4 kg/eq). Our findings can underscore the potential of EF toward selective SA production, which can be used in the bio-based SA-producing industries where product selectivity and down-streaming are crucial challenges.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
2,5-Furandicarboxylic acid (FDCA), derived from the oxidation of 5-hydroxymethylfurfural (HMF), is emerging as a viable biomass-based monomer for bioplastic production, offering a sustainable alternative to a petroleum-derived monomer. This study systematically investigates lattice oxygen (OL) activation in Mn-based oxides through doping with transition metals (Ce, Zr, La, and Sm) to enhance the aerobic oxidation of HMF to FDCA. Among the prepared catalysts, Mn6Ce1Ox (Mn/Ce molar ratio of 6), with the highest surface oxygen vacancy (OV) concentration and activated OL, achieved a high FDCA yield of 97.2% with a generation rate of 1520 μmolFDCA gcat–1 h–1 under mild conditions (120 °C, 1 MPa O2, 8 h). Catalyst characterization results revealed that the metal dopants modulated the strength of Mn–O bonds, thereby influencing OL activity and OV concentration. Incorporating Ce ions into the MnOx lattice weakened Mn–O bond strength, enhancing OL mobility and promoting OV formation. This reactive OL, acting as the active oxygen species for HMF oxidation, could be efficiently regenerated via the Mars–van Krevelen mechanism. The abundant OV on Mn6Ce1Ox promoted the adsorption of both O2 and HMF. The synergistic roles of OV and OL contributed to the high activity of this catalyst in converting HMF to FDCA. This study provides critical insights into the strategic regulation of OL activity in Mn-based oxides, offering promising avenues for improving the efficiency and cost-effectiveness of biomass-based chemical production via catalytic oxidation.
{"title":"Strategic Metal Doping in MnOx Catalysts Unlocks High-Yield 2,5-Furandicarboxylic Acid Production via Tailored Lattice Oxygen Activity and Oxygen Vacancies","authors":"Qing Liu, Yuan Gong, Jing Zeng, Yinghong Zhao, Jia Lv, Zhicheng Jiang, Changwei Hu, Yingdong Zhou","doi":"10.1021/acssuschemeng.4c09055","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09055","url":null,"abstract":"2,5-Furandicarboxylic acid (FDCA), derived from the oxidation of 5-hydroxymethylfurfural (HMF), is emerging as a viable biomass-based monomer for bioplastic production, offering a sustainable alternative to a petroleum-derived monomer. This study systematically investigates lattice oxygen (O<sub>L</sub>) activation in Mn-based oxides through doping with transition metals (Ce, Zr, La, and Sm) to enhance the aerobic oxidation of HMF to FDCA. Among the prepared catalysts, Mn<sub>6</sub>Ce<sub>1</sub>O<sub><i>x</i></sub> (Mn/Ce molar ratio of 6), with the highest surface oxygen vacancy (O<sub>V</sub>) concentration and activated O<sub>L</sub>, achieved a high FDCA yield of 97.2% with a generation rate of 1520 μmol<sub>FDCA</sub> g<sub>cat</sub><sup>–1</sup> h<sup>–1</sup> under mild conditions (120 °C, 1 MPa O<sub>2</sub>, 8 h). Catalyst characterization results revealed that the metal dopants modulated the strength of Mn–O bonds, thereby influencing O<sub>L</sub> activity and O<sub>V</sub> concentration. Incorporating Ce ions into the MnO<sub><i>x</i></sub> lattice weakened Mn–O bond strength, enhancing O<sub>L</sub> mobility and promoting O<sub>V</sub> formation. This reactive O<sub>L</sub>, acting as the active oxygen species for HMF oxidation, could be efficiently regenerated via the Mars–van Krevelen mechanism. The abundant O<sub>V</sub> on Mn<sub>6</sub>Ce<sub>1</sub>O<sub><i>x</i></sub> promoted the adsorption of both O<sub>2</sub> and HMF. The synergistic roles of O<sub>V</sub> and O<sub>L</sub> contributed to the high activity of this catalyst in converting HMF to FDCA. This study provides critical insights into the strategic regulation of O<sub>L</sub> activity in Mn-based oxides, offering promising avenues for improving the efficiency and cost-effectiveness of biomass-based chemical production via catalytic oxidation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142991589","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-21DOI: 10.1021/acssuschemeng.4c08391
Åke Henrik-Klemens, Ulrica Edlund, Gunnar Westman, Anette Larsson
The high glass transition temperature (Tg), stiffness, and poor flow properties of lignin are obstacles to lignin and lignocellulose utilization in thermoplastic applications. Two commonly applied methods to modify the viscoelastic properties of polymers are external plasticization, which involves physically blending them with low-molecular-weight additives, and internal plasticization, which involves covalently attaching side chains. However, most studies on lignin plasticization have focused on either technical, low-molecular-weight lignin or native, in situ lignin, with few efforts to bridge this gap. This study aims to determine if different lignin structures are susceptible to different modes of plasticization and how the plasticizer affects the phase morphology of the blends. Four lignins (softwood kraft lignin and lignin isolated from wheat straw, Norway spruce xylem, and residual softwood kraft pulp lignin) were plasticized with three external plasticizers (glycerol, triacetin, and diethyl phthalate) with different functionalities. The four lignins were in parallel internally plasticized by esterification with short-chain fatty acids (acetic, propionic, and butyric acid). The Tg and phase morphology of the modified lignins were studied by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). Apart from phase separation in some lignin plasticizer blends, each plasticizer demonstrated similar efficiency (Tg depression) across all lignins, suggesting that the structure of the plasticizer, rather than the lignin structure, plays a more significant role in determining the outcome. Aprotic plasticizers were generally more efficient than protic per molar unit, and the magnitude of their mechanical dampening was also smaller over the glass transition, likely due to a decrease in the hydrogen bond density of the system. External plasticization was also found to narrow the width of the glass transition, indicating the formation of a morphologically more homogeneous material with less local Tgs than the pure lignin, whereas esterification broadened it somewhat.
{"title":"Dynamic Mechanical Analysis of Plasticized and Esterified Native, Residual, and Technical Lignins: Compatibility and Glass Transition","authors":"Åke Henrik-Klemens, Ulrica Edlund, Gunnar Westman, Anette Larsson","doi":"10.1021/acssuschemeng.4c08391","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08391","url":null,"abstract":"The high glass transition temperature (<i>T</i><sub>g</sub>), stiffness, and poor flow properties of lignin are obstacles to lignin and lignocellulose utilization in thermoplastic applications. Two commonly applied methods to modify the viscoelastic properties of polymers are external plasticization, which involves physically blending them with low-molecular-weight additives, and internal plasticization, which involves covalently attaching side chains. However, most studies on lignin plasticization have focused on either technical, low-molecular-weight lignin or native, in situ lignin, with few efforts to bridge this gap. This study aims to determine if different lignin structures are susceptible to different modes of plasticization and how the plasticizer affects the phase morphology of the blends. Four lignins (softwood kraft lignin and lignin isolated from wheat straw, Norway spruce xylem, and residual softwood kraft pulp lignin) were plasticized with three external plasticizers (glycerol, triacetin, and diethyl phthalate) with different functionalities. The four lignins were in parallel internally plasticized by esterification with short-chain fatty acids (acetic, propionic, and butyric acid). The <i>T</i><sub>g</sub> and phase morphology of the modified lignins were studied by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). Apart from phase separation in some lignin plasticizer blends, each plasticizer demonstrated similar efficiency (<i>T</i><sub>g</sub> depression) across all lignins, suggesting that the structure of the plasticizer, rather than the lignin structure, plays a more significant role in determining the outcome. Aprotic plasticizers were generally more efficient than protic per molar unit, and the magnitude of their mechanical dampening was also smaller over the glass transition, likely due to a decrease in the hydrogen bond density of the system. External plasticization was also found to narrow the width of the glass transition, indicating the formation of a morphologically more homogeneous material with less local <i>T</i><sub>g</sub>s than the pure lignin, whereas esterification broadened it somewhat.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142991586","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Expanded polystyrene (EPS) is commonly used in everyday life for packaging, construction materials, and household appliances. However, EPS waste contributes significantly to environmental pollution due to its nonbiodegradable nature. To address this issue, the utilizing EPS waste to produce nonwoven fabric has been explored as a potential recycling solution to reduce its environmental impact. In this study, EPS waste was dissolved in acetone as a solvent to facilitate degassing, after which the solvent was evaporated. The remaining material was ground into smaller particles and formed into fibers using varying air pressures (0.2–0.5 psi) in the melt jet spinning process. The fibers were subsequently compressed into specimens through hot-pressing for testing. The results showed that higher air pressures produced finer fibers, which significantly improved thermal conductivity and penetration resistance, while air permeability decreased. Thermal properties exhibited minor changes without a clear trend. This research highlights the potential of utilizing recycled EPS waste for applications such as filters, ceiling panels and soilless farming materials, contributing to sustainable waste management practices.
{"title":"Sustainable Conversion of Expanded Polystyrene Waste into Nonwoven Fabric Using the Melt Jet Spinning Process: Characterization and Properties","authors":"Ektinai Jansri, Nanjaporn Roungpaisan, Sommai Pivsa-Art, Piyaporn Kampeerapappun","doi":"10.1021/acssuschemeng.4c09595","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09595","url":null,"abstract":"Expanded polystyrene (EPS) is commonly used in everyday life for packaging, construction materials, and household appliances. However, EPS waste contributes significantly to environmental pollution due to its nonbiodegradable nature. To address this issue, the utilizing EPS waste to produce nonwoven fabric has been explored as a potential recycling solution to reduce its environmental impact. In this study, EPS waste was dissolved in acetone as a solvent to facilitate degassing, after which the solvent was evaporated. The remaining material was ground into smaller particles and formed into fibers using varying air pressures (0.2–0.5 psi) in the melt jet spinning process. The fibers were subsequently compressed into specimens through hot-pressing for testing. The results showed that higher air pressures produced finer fibers, which significantly improved thermal conductivity and penetration resistance, while air permeability decreased. Thermal properties exhibited minor changes without a clear trend. This research highlights the potential of utilizing recycled EPS waste for applications such as filters, ceiling panels and soilless farming materials, contributing to sustainable waste management practices.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"74 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989971","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-20DOI: 10.1021/acssuschemeng.4c08332
Yingkui Yan, Ye Wang, Chenxiang Peng, Jing Wang, Xusheng Wang, Li Shi
The exploration of single-atom catalysts (SACs) with unique coordination structures is of vital importance for boosting photocatalytic CO2 reduction, yet it remains challenging. Herein, we develop a novel SAC with a unique asymmetric coordination structure of the Ni catalytic site, which can trap photogenerated electrons to realize highly efficient photocatalytic CO2 reduction in the presence of triethanolamine as an electron donor. Doping a B heteroatom into the N-doped carbon substrate would introduce B–N bond and meanwhile create defects, thus providing a feasible strategy to break the symmetry of the Ni–N4 moiety and finally producing a coordination unsaturated Ni–N3–B structure. It is demonstrated that the asymmetric Ni–N3–B species can improve the electron trapping ability and reduce the formation energy barrier of the *COOH intermediate compared with the symmetric Ni–N4 species for boosting photocatalytic CO2 reduction. Such a concept of breaking the symmetric coordination structure of SACs could provide a promising approach for constructing effective catalytic sites toward solar energy-driven conversion.
{"title":"Single-Atom Ni Sites with Asymmetric Coordination Structures for Efficient Photocatalytic CO2 Reduction","authors":"Yingkui Yan, Ye Wang, Chenxiang Peng, Jing Wang, Xusheng Wang, Li Shi","doi":"10.1021/acssuschemeng.4c08332","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08332","url":null,"abstract":"The exploration of single-atom catalysts (SACs) with unique coordination structures is of vital importance for boosting photocatalytic CO<sub>2</sub> reduction, yet it remains challenging. Herein, we develop a novel SAC with a unique asymmetric coordination structure of the Ni catalytic site, which can trap photogenerated electrons to realize highly efficient photocatalytic CO<sub>2</sub> reduction in the presence of triethanolamine as an electron donor. Doping a B heteroatom into the N-doped carbon substrate would introduce B–N bond and meanwhile create defects, thus providing a feasible strategy to break the symmetry of the Ni–N<sub>4</sub> moiety and finally producing a coordination unsaturated Ni–N<sub>3</sub>–B structure. It is demonstrated that the asymmetric Ni–N<sub>3</sub>–B species can improve the electron trapping ability and reduce the formation energy barrier of the <sup>*</sup>COOH intermediate compared with the symmetric Ni–N<sub>4</sub> species for boosting photocatalytic CO<sub>2</sub> reduction. Such a concept of breaking the symmetric coordination structure of SACs could provide a promising approach for constructing effective catalytic sites toward solar energy-driven conversion.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"45 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142991590","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-19DOI: 10.1021/acssuschemeng.4c04952
M. Aaddouz, F. Laoutid, J. Mariage, B. Yada, A. Toncheva, J. Lazko, K. Azzaoui, R. Sabbahi, E. Mejdoubi, M. R. Saeb, Ph Dubois
Tannic acid (TA) is an abundant biobased aromatic compound that can form char under thermal degradation and fire conditions. In the present study, TA was chemically modified by grafting potassium phosphate groups using a two-step process, requiring neither heating nor organic solvents. Initially, TA was functionalized through ball-milling mechanochemistry in the presence of P2O5 to graft phosphoric acid, which was later converted to potassium phosphate salt by simple precipitation in water in the presence of KOH. The reaction yield was 87%. The resulting product, namely, TA-P-K, was used as a flame retardant (FR) in polypropylene (PP). At 30 wt %, TA-P-K was dispersed in PP by melt processing, resulting in a significant reduction in the peak heat release rate of 78% measured by the mass loss cone calorimeter test. Additionally, an intumescent residue was formed during combustion, which protected the material. In terms of flame-retardancy performance, the polymer composite took a “Good” label based on Flame-Retardancy Index (FRI), which seems promising in view of FR being fully biobased.
{"title":"Mechanochemistry for the Synthesis of a Sustainable Phosphorus/Potassium Tannic Acid Flame-Retardant Additive and Its Application in Polypropylene","authors":"M. Aaddouz, F. Laoutid, J. Mariage, B. Yada, A. Toncheva, J. Lazko, K. Azzaoui, R. Sabbahi, E. Mejdoubi, M. R. Saeb, Ph Dubois","doi":"10.1021/acssuschemeng.4c04952","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c04952","url":null,"abstract":"Tannic acid (TA) is an abundant biobased aromatic compound that can form char under thermal degradation and fire conditions. In the present study, TA was chemically modified by grafting potassium phosphate groups using a two-step process, requiring neither heating nor organic solvents. Initially, TA was functionalized through ball-milling mechanochemistry in the presence of P<sub>2</sub>O<sub>5</sub> to graft phosphoric acid, which was later converted to potassium phosphate salt by simple precipitation in water in the presence of KOH. The reaction yield was 87%. The resulting product, namely, TA-P-K, was used as a flame retardant (FR) in polypropylene (PP). At 30 wt %, TA-P-K was dispersed in PP by melt processing, resulting in a significant reduction in the peak heat release rate of 78% measured by the mass loss cone calorimeter test. Additionally, an intumescent residue was formed during combustion, which protected the material. In terms of flame-retardancy performance, the polymer composite took a “<i>Good</i>” label based on <i>Flame-Retardancy Index</i> (<i>FRI</i>), which seems promising in view of FR being fully biobased.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989972","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-16DOI: 10.1021/acssuschemeng.4c10171
Hiba Azim, Amy-Louise Johnston, Morag Nixon, John Luke Woodliffe, Romano Theunissen, Reshma Suresh, Subarna Sivapalan, Jack Bobo, Peter Licence
We illustrate the importance of early career perspectives and diverse partnerships to develop solutions and overcome key challenges to achieve the Sustainable Development Goals.
{"title":"Collaborating for Impact: Navigating Partnerships and Overcoming Challenges across the Sustainable Development Goals","authors":"Hiba Azim, Amy-Louise Johnston, Morag Nixon, John Luke Woodliffe, Romano Theunissen, Reshma Suresh, Subarna Sivapalan, Jack Bobo, Peter Licence","doi":"10.1021/acssuschemeng.4c10171","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c10171","url":null,"abstract":"We illustrate the importance of early career perspectives and diverse partnerships to develop solutions and overcome key challenges to achieve the Sustainable Development Goals.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"127 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986021","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-16DOI: 10.1021/acssuschemeng.4c07538
Andrea Torre-Celeizabal, Francesca Russo, Francesco Galiano, Alberto Figoli, Clara Casado-Coterillo, Aurora Garea
Although membrane technology is widely used in different gas separation applications, membrane manufacturers need to reduce the environmental impact during the membrane fabrication process within the framework of the circular economy by replacing toxic solvents, oil-based polymers, and such by more sustainable alternatives. These include environmentally friendly materials, such as biopolymers, green solvents, and surfactant free porous fillers. This work promotes the use of environmentally sustainable and low toxic alternatives, introducing the novel application of cellulose acetate (CA) as a biopolymer in combination with dimethyl carbonate (DMC) as a greener solvent and different inorganic fillers (Zeolite-A, ETS-10, AM-4 and ZIF-8) prepared without the use of toxic solvents or reactants. Hansen Solubility Parameters were used to confirm the polymer–solvent affinity. Pure CA and mixed matrix membranes were characterized regarding their hydrophilicity by water uptake and contact angle measurements, thermal stability by TGA, mechanical resistance, ATR-FTIR and scanning electron microscopy before evaluating the gas separation performance by single gas permeability of N2, CH4, and CO2. Conditioning of the CA membranes is observed causing reduction of the CO2 permeability values from 12,600 Barrer for the fresh 0.5 wt % ETS-10/CA membrane to 740 Barrer for the 0.5 wt % ZIF-8/CA membranes, corresponding to 24% and 4.2% reductions in CO2/CH4 selectivity and 30% and 24% increase in CO2/N2 selectivity for the same membranes. The structure–relationship was evaluated by phenomenological models which are useful at low filler loading considering flux direction and particle shape and size but still fail to explain the interactions between the DMC green solvent and CA matrix and fillers that are influencing gas transport performance different than other CA membranes.
{"title":"Green Synthesis of Cellulose Acetate Mixed Matrix Membranes: Structure–Function Characterization","authors":"Andrea Torre-Celeizabal, Francesca Russo, Francesco Galiano, Alberto Figoli, Clara Casado-Coterillo, Aurora Garea","doi":"10.1021/acssuschemeng.4c07538","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07538","url":null,"abstract":"Although membrane technology is widely used in different gas separation applications, membrane manufacturers need to reduce the environmental impact during the membrane fabrication process within the framework of the circular economy by replacing toxic solvents, oil-based polymers, and such by more sustainable alternatives. These include environmentally friendly materials, such as biopolymers, green solvents, and surfactant free porous fillers. This work promotes the use of environmentally sustainable and low toxic alternatives, introducing the novel application of cellulose acetate (CA) as a biopolymer in combination with dimethyl carbonate (DMC) as a greener solvent and different inorganic fillers (Zeolite-A, ETS-10, AM-4 and ZIF-8) prepared without the use of toxic solvents or reactants. Hansen Solubility Parameters were used to confirm the polymer–solvent affinity. Pure CA and mixed matrix membranes were characterized regarding their hydrophilicity by water uptake and contact angle measurements, thermal stability by TGA, mechanical resistance, ATR-FTIR and scanning electron microscopy before evaluating the gas separation performance by single gas permeability of N<sub>2</sub>, CH<sub>4</sub>, and CO<sub>2</sub>. Conditioning of the CA membranes is observed causing reduction of the CO<sub>2</sub> permeability values from 12,600 Barrer for the fresh 0.5 wt % ETS-10/CA membrane to 740 Barrer for the 0.5 wt % ZIF-8/CA membranes, corresponding to 24% and 4.2% reductions in CO<sub>2</sub>/CH<sub>4</sub> selectivity and 30% and 24% increase in CO<sub>2</sub>/N<sub>2</sub> selectivity for the same membranes. The structure–relationship was evaluated by phenomenological models which are useful at low filler loading considering flux direction and particle shape and size but still fail to explain the interactions between the DMC green solvent and CA matrix and fillers that are influencing gas transport performance different than other CA membranes.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-16DOI: 10.1021/acssuschemeng.4c07408
Yuanhui Yao, Kai Wei, Shuang Zhao, Haiqiao Zhou, Bin Kui, Genping Zhu, Wei Wang, Peng Gao, Wei Ye
Electrocatalytically converting nitrates in sewage to ammonia, which can not only achieve the purpose of eliminating sewage but also obtaining valuable ammonia, is an effective supplement to the traditional Haber–Bosch process. Although significant progress has been made in cathodic catalyst design, the overall ammonia electrolysis from nitrate reduction is still restricted by the anodic oxygen evolution heavily relying on noble-based catalysts. Herein, a bimetallic NiFe-MOF nanosheet array electrode is fabricated and serves as an efficient bifunctional catalyst for nitrate reduction and oxygen evolution reactions. The introduction of Fe to Ni-MOF facilitates the formation of a nanosheet structure with higher electrochemical active surface area, as well as provides synergetic NiFe sites. The NiFe-MOF electrode reaches a greatly enhanced ammonia yield rate of 0.94 mmol cm–2 h–1 and a Faradaic efficiency of 90.8% at the cathode and −0.6 V versus reversible hydrogen electrode, as well as an enhanced oxygen evolution reaction with a declined overpotential of 424 mV at 50 mA cm–2. As a bifunctional catalyst in the overall electrocatalysis, the performance of NiFe-MOF in the nitrate reduction reaction is comparable with that using Pt mesh as a counter electrode.
{"title":"Highly Efficient Bifunctional NiFe-MOF Array Electrode for Nitrate Reduction to Ammonia and Oxygen Evolution Reactions","authors":"Yuanhui Yao, Kai Wei, Shuang Zhao, Haiqiao Zhou, Bin Kui, Genping Zhu, Wei Wang, Peng Gao, Wei Ye","doi":"10.1021/acssuschemeng.4c07408","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07408","url":null,"abstract":"Electrocatalytically converting nitrates in sewage to ammonia, which can not only achieve the purpose of eliminating sewage but also obtaining valuable ammonia, is an effective supplement to the traditional Haber–Bosch process. Although significant progress has been made in cathodic catalyst design, the overall ammonia electrolysis from nitrate reduction is still restricted by the anodic oxygen evolution heavily relying on noble-based catalysts. Herein, a bimetallic NiFe-MOF nanosheet array electrode is fabricated and serves as an efficient bifunctional catalyst for nitrate reduction and oxygen evolution reactions. The introduction of Fe to Ni-MOF facilitates the formation of a nanosheet structure with higher electrochemical active surface area, as well as provides synergetic NiFe sites. The NiFe-MOF electrode reaches a greatly enhanced ammonia yield rate of 0.94 mmol cm<sup>–2</sup> h<sup>–1</sup> and a Faradaic efficiency of 90.8% at the cathode and −0.6 V versus reversible hydrogen electrode, as well as an enhanced oxygen evolution reaction with a declined overpotential of 424 mV at 50 mA cm<sup>–2</sup>. As a bifunctional catalyst in the overall electrocatalysis, the performance of NiFe-MOF in the nitrate reduction reaction is comparable with that using Pt mesh as a counter electrode.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"77 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986105","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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