Pub Date : 2025-03-31DOI: 10.1021/acssuschemeng.5c00543
Lu Zhang, Ming-Yi Sun, Xiang-Yu Li, Meng-Yuan Liu, Hong-Yu Chu, Chong-Chen Wang, Peng Wang, Xiao-Hong Yi, Yi Wang, Jiguang Deng
An environmentally friendly adsorbent for recovering nuclear energy source U(VI) from wastewater plays a crucial role in resource recovery and environmental preservation. In this work, a double-network aerogel adsorbent composite constructed from sodium alginate, poly(acrylic acid), and NH2-MIL-125 (NM@SA) was fabricated by a mild method, which was adopted to remove and concentrate U(VI) in the corresponding simulated wastewater samples. According to the results of adsorption kinetic and isotherm models, the adsorption of U(VI) on NM@SA was a monolayer chemisorption process. The maximum adsorption capacity of NM@SA for U(VI) calculated from the Langmuir model was 703.6 mg·g–1. In addition, the adsorbent maintained excellent adsorption capacity, recoverability, and reuse in large-scale operation. The same abilities can be demonstrated in real seawater environments. Finally, the potential adsorption mechanisms of U(VI) on NM@SA were discussed in conjunction with the experimental determination and characterization results. Overall, this study introduces an advantageous research approach for treating U(VI)-containing radioactive wastewater.
{"title":"Uranium Extraction from Radioactive Wastewater by NH2-MIL-125 Immobilized in a Double-Network Aerogel Microsphere","authors":"Lu Zhang, Ming-Yi Sun, Xiang-Yu Li, Meng-Yuan Liu, Hong-Yu Chu, Chong-Chen Wang, Peng Wang, Xiao-Hong Yi, Yi Wang, Jiguang Deng","doi":"10.1021/acssuschemeng.5c00543","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00543","url":null,"abstract":"An environmentally friendly adsorbent for recovering nuclear energy source U(VI) from wastewater plays a crucial role in resource recovery and environmental preservation. In this work, a double-network aerogel adsorbent composite constructed from sodium alginate, poly(acrylic acid), and NH<sub>2</sub>-MIL-125 (NM@SA) was fabricated by a mild method, which was adopted to remove and concentrate U(VI) in the corresponding simulated wastewater samples. According to the results of adsorption kinetic and isotherm models, the adsorption of U(VI) on NM@SA was a monolayer chemisorption process. The maximum adsorption capacity of NM@SA for U(VI) calculated from the Langmuir model was 703.6 mg·g<sup>–1</sup>. In addition, the adsorbent maintained excellent adsorption capacity, recoverability, and reuse in large-scale operation. The same abilities can be demonstrated in real seawater environments. Finally, the potential adsorption mechanisms of U(VI) on NM@SA were discussed in conjunction with the experimental determination and characterization results. Overall, this study introduces an advantageous research approach for treating U(VI)-containing radioactive wastewater.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"40 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737034","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 : 2025-03-29DOI: 10.1021/acssuschemeng.4c10101
Mairui Zhang, Linjing Jia, Mi Li, Haixin Peng, Ying Tan, Shubhangi Arvelli, Ye Huang, Adriana C. Neves, Eun Joong Oh, Jikai Zhao
This study presents a novel and cost-effective approach to biomass pretreatment that addresses the limitations of conventional methods, which often result in high water and chemical usage as well as the production of chemical-laden wastewater. We investigated the integration of metal oxides (specifically CaO and MgO) for biomass pretreatment and mineral acids (H2SO4 or H3PO4) for pH adjustment at a high solid loading of 20 wt %. This innovative method allows for direct enzymatic hydrolysis and fermentation of the resulting slurry, effectively eliminating the need for solid–liquid separation and extensive washing. Our findings reveal that hydrolysates from MgO combined with H3PO4 or H2SO4 were inhibitory to Saccharomyces cerevisiae, resulting in no ethanol production. In contrast, corn stover that was pretreated with CaO and subsequently adjusted to pH with H3PO4 demonstrated a higher enzymatic hydrolysis efficiency than the case of adjusting pH with H2SO4, achieving over 65% glucan conversion and 80% xylan conversion, along with an ethanol concentration of approximately 33 g/L following separate hydrolysis and fermentation. This enhanced performance can be attributed to reduced osmotic stress, decreased salt toxicity, and minimal formation of inhibitors, as CaO neutralized with H3PO4 generated the minimally soluble precipitate Ca3(PO4)2. Furthermore, employing a semisimultaneous saccharification and fermentation process improved sugar utilization efficiency, resulting in an increased ethanol concentration of 46 g/L. The corn stover fermentation residue (CSFR) contained 93% lignin, predominantly of syringyl and guaiacyl types. This study offers a sustainable and scalable method for producing cellulosic ethanol, significantly lowering chemical and water consumption while achieving a high conversion efficiency.
{"title":"One-Pot Biomass Pretreatment for Ethanol Production by Engineered Saccharomyces cerevisiae","authors":"Mairui Zhang, Linjing Jia, Mi Li, Haixin Peng, Ying Tan, Shubhangi Arvelli, Ye Huang, Adriana C. Neves, Eun Joong Oh, Jikai Zhao","doi":"10.1021/acssuschemeng.4c10101","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c10101","url":null,"abstract":"This study presents a novel and cost-effective approach to biomass pretreatment that addresses the limitations of conventional methods, which often result in high water and chemical usage as well as the production of chemical-laden wastewater. We investigated the integration of metal oxides (specifically CaO and MgO) for biomass pretreatment and mineral acids (H<sub>2</sub>SO<sub>4</sub> or H<sub>3</sub>PO<sub>4</sub>) for pH adjustment at a high solid loading of 20 wt %. This innovative method allows for direct enzymatic hydrolysis and fermentation of the resulting slurry, effectively eliminating the need for solid–liquid separation and extensive washing. Our findings reveal that hydrolysates from MgO combined with H<sub>3</sub>PO<sub>4</sub> or H<sub>2</sub>SO<sub>4</sub> were inhibitory to <i>Saccharomyces cerevisiae</i>, resulting in no ethanol production. In contrast, corn stover that was pretreated with CaO and subsequently adjusted to pH with H<sub>3</sub>PO<sub>4</sub> demonstrated a higher enzymatic hydrolysis efficiency than the case of adjusting pH with H<sub>2</sub>SO<sub>4</sub>, achieving over 65% glucan conversion and 80% xylan conversion, along with an ethanol concentration of approximately 33 g/L following separate hydrolysis and fermentation. This enhanced performance can be attributed to reduced osmotic stress, decreased salt toxicity, and minimal formation of inhibitors, as CaO neutralized with H<sub>3</sub>PO<sub>4</sub> generated the minimally soluble precipitate Ca<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>. Furthermore, employing a semisimultaneous saccharification and fermentation process improved sugar utilization efficiency, resulting in an increased ethanol concentration of 46 g/L. The corn stover fermentation residue (CSFR) contained 93% lignin, predominantly of syringyl and guaiacyl types. This study offers a sustainable and scalable method for producing cellulosic ethanol, significantly lowering chemical and water consumption while achieving a high conversion efficiency.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"72 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734100","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 : 2025-03-29DOI: 10.1021/acssuschemeng.5c00435
Shi-Qian Bian, Zikai Wang, Jin-Song Gong, Chang Su, Heng Li, Zheng-Hong Xu, Jin-Song Shi
Nitrilase has attracted widespread attention due to its efficiency, specificity, and ecofriendliness in the hydrolysis reactions of nitrile compounds. These enzymes can catalyze various substrates, including aliphatic nitriles and aromatic nitriles. However, high substrate specificity is key to efficient catalysis and high-purity product synthesis. This study aims to enhance the preference of nitrilase for aliphatic nitriles through substrate channel engineering to expand its industrial applications. We developed a semirational design workflow that integrates extensive search and deep optimization strategies, relying on computational tools such as substrate channel modeling and molecular docking to systematically identify and optimize key amino acid residues related to substrate binding. Taking 3-chloropropionitrile as an example, the specific activity of the optimal mutant G191A/L194W increased from 2.47 to 58.35 U·mg–1, with the substrate conversion rate approaching 100%, while the catalytic activity toward aromatic nitriles significantly decreased. Molecular dynamics simulations revealed the correlation between substrate specificity and channel morphology regulated by W194 and promoted the formation of a specificity-enhanced mutant network. This study provides a structural and mechanistic basis for substrate channel design and enzyme function modification and validates its potential for industrial applications.
{"title":"Enhancing the Substrate Specificity of Nitrilase toward Aliphatic Nitriles Based on Substrate Channel Design","authors":"Shi-Qian Bian, Zikai Wang, Jin-Song Gong, Chang Su, Heng Li, Zheng-Hong Xu, Jin-Song Shi","doi":"10.1021/acssuschemeng.5c00435","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00435","url":null,"abstract":"Nitrilase has attracted widespread attention due to its efficiency, specificity, and ecofriendliness in the hydrolysis reactions of nitrile compounds. These enzymes can catalyze various substrates, including aliphatic nitriles and aromatic nitriles. However, high substrate specificity is key to efficient catalysis and high-purity product synthesis. This study aims to enhance the preference of nitrilase for aliphatic nitriles through substrate channel engineering to expand its industrial applications. We developed a semirational design workflow that integrates extensive search and deep optimization strategies, relying on computational tools such as substrate channel modeling and molecular docking to systematically identify and optimize key amino acid residues related to substrate binding. Taking 3-chloropropionitrile as an example, the specific activity of the optimal mutant G191A/L194W increased from 2.47 to 58.35 U·mg<sup>–1</sup>, with the substrate conversion rate approaching 100%, while the catalytic activity toward aromatic nitriles significantly decreased. Molecular dynamics simulations revealed the correlation between substrate specificity and channel morphology regulated by W194 and promoted the formation of a specificity-enhanced mutant network. This study provides a structural and mechanistic basis for substrate channel design and enzyme function modification and validates its potential for industrial applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"2 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736376","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 : 2025-03-28DOI: 10.1021/acssuschemeng.5c00832
Yu Zhang, Zhenyu Hu, Yiyang Bi, Songlin Tian, Haoran Sun, Kai Li, Wanqiang Liu, Lianshan Sun, Wei Liu, Dong Wang
Dendrite growth, corrosion, and side reactions on zinc anodes significantly hinder the commercialization of aqueous zinc-ion batteries (AZIBs). To address these challenges, we propose a simple and cost-effective room-temperature cold-pressing process to build dendrite-free zinc anodes by means of a special collector-composite structure. Specifically, the symmetric cell assembled with copper mesh (CM) based Zn anodes exhibited remarkable cycling stability over 4000 h at 1 mA cm–2 current density and also exhibited an exceptionally long life of over 2800 h at 5 mA cm–2 current density, reflecting the Stability of Zn zinc plating/stripping cycles. In situ optical microscopy was employed to investigate the deposition behavior of the CM electrode during repeated plating and stripping processes. Density functional theory (DFT) calculates that Zn2+ ions are preferentially adsorbed on the copper surface, while COMSOL simulation elucidates the homogeneous electric field and current density distribution due to the unique three-dimensional structure of the CM electrode. These synergistic effects effectively inhibited the growth of dendrites, ensuring a stable zinc deposition process. This work provides a scalable approach for designing dendrite-free zinc anodes for practical AZIB applications.
{"title":"Cold-Pressing Strategy for Constructing Simple and High-Performance Dendrite-Free Zinc Anodes for Aqueous Zinc-Ion Batteries","authors":"Yu Zhang, Zhenyu Hu, Yiyang Bi, Songlin Tian, Haoran Sun, Kai Li, Wanqiang Liu, Lianshan Sun, Wei Liu, Dong Wang","doi":"10.1021/acssuschemeng.5c00832","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00832","url":null,"abstract":"Dendrite growth, corrosion, and side reactions on zinc anodes significantly hinder the commercialization of aqueous zinc-ion batteries (AZIBs). To address these challenges, we propose a simple and cost-effective room-temperature cold-pressing process to build dendrite-free zinc anodes by means of a special collector-composite structure. Specifically, the symmetric cell assembled with copper mesh (CM) based Zn anodes exhibited remarkable cycling stability over 4000 h at 1 mA cm<sup>–2</sup> current density and also exhibited an exceptionally long life of over 2800 h at 5 mA cm<sup>–2</sup> current density, reflecting the Stability of Zn zinc plating/stripping cycles. In situ optical microscopy was employed to investigate the deposition behavior of the CM electrode during repeated plating and stripping processes. Density functional theory (DFT) calculates that Zn<sup>2+</sup> ions are preferentially adsorbed on the copper surface, while COMSOL simulation elucidates the homogeneous electric field and current density distribution due to the unique three-dimensional structure of the CM electrode. These synergistic effects effectively inhibited the growth of dendrites, ensuring a stable zinc deposition process. This work provides a scalable approach for designing dendrite-free zinc anodes for practical AZIB applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723601","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 : 2025-03-28DOI: 10.1021/acssuschemeng.5c00297
Chenyu Zhao, Meihan Liu, Xiaoye Liu, Xinxuan Yang, Lin Fan, Maobin Wei, Huilian Liu, Xin Li, Tie Liu, Bin Li, Jinghai Yang, Fengyou Wang, Lili Yang
Perovskite solar cells (PSCs) employing a SnO2 electron transport layer (ETL) have consistently broken efficiency records over the past decade by developing new active materials and optimizing device structures. As a key functional layer of PSCs, the SnO2 ETL directly dictates the performance and stability of the entire device. However, the defect-induced recombination losses and the optical losses caused by suboptimal optical paths on the SnO2/perovskite interface remain major barriers to PSCs performance improvement. Therefore, from the perspective of interfacial engineering, this study designs and synthesizes a metal–organic framework (MOF) material based on tin sulfate (SnSO4) and 2-nitroterephthalic acid (NTA), namely, Sn-NTA, which combines the functions of regulating the incident optical path and passivating interface defects. The Sn-NTA nanocluster enhances light scattering at the SnO2/perovskite interface, thus increasing perovskite light absorption. Moreover, the mesoporous MOF with carboxyl groups templates the crystallization of the perovskite and enables the formation of a radial MOF/perovskite junction, accelerating charge transfer. As a result, devices based on Sn-NTA show significantly improved photovoltaic properties, achieving a high power conversion efficiency of 24.04%. This work not only provides a new method for preparing multifunctional MOF materials but also inspires future researchers to focus on the collaborative design of interface optical structures and defect termination.
{"title":"Synergistic Enhancement of Light Harvesting and Interfacial Defect Reduction Using Metal–Organic Frameworks for Efficient and Stable Perovskite Solar Cells","authors":"Chenyu Zhao, Meihan Liu, Xiaoye Liu, Xinxuan Yang, Lin Fan, Maobin Wei, Huilian Liu, Xin Li, Tie Liu, Bin Li, Jinghai Yang, Fengyou Wang, Lili Yang","doi":"10.1021/acssuschemeng.5c00297","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00297","url":null,"abstract":"Perovskite solar cells (PSCs) employing a SnO<sub>2</sub> electron transport layer (ETL) have consistently broken efficiency records over the past decade by developing new active materials and optimizing device structures. As a key functional layer of PSCs, the SnO<sub>2</sub> ETL directly dictates the performance and stability of the entire device. However, the defect-induced recombination losses and the optical losses caused by suboptimal optical paths on the SnO<sub>2</sub>/perovskite interface remain major barriers to PSCs performance improvement. Therefore, from the perspective of interfacial engineering, this study designs and synthesizes a metal–organic framework (MOF) material based on tin sulfate (SnSO<sub>4</sub>) and 2-nitroterephthalic acid (NTA), namely, Sn-NTA, which combines the functions of regulating the incident optical path and passivating interface defects. The Sn-NTA nanocluster enhances light scattering at the SnO<sub>2</sub>/perovskite interface, thus increasing perovskite light absorption. Moreover, the mesoporous MOF with carboxyl groups templates the crystallization of the perovskite and enables the formation of a radial MOF/perovskite junction, accelerating charge transfer. As a result, devices based on Sn-NTA show significantly improved photovoltaic properties, achieving a high power conversion efficiency of 24.04%. This work not only provides a new method for preparing multifunctional MOF materials but also inspires future researchers to focus on the collaborative design of interface optical structures and defect termination.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"89 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723597","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 : 2025-03-28DOI: 10.1021/acssuschemeng.4c09745
Izabela Silva Freitas, Aryane Maria de Oliveira Lima, Edson de Paiva Alves, Genes de Morais Souza, Luiz Antônio Magalhães Pontes
Acetonitrile (ACN) is a valuable product, serving as a feedstock in the petrochemical, pharmaceutical, and fine chemical industries. This study analyzes the environmental footprint of ACN production employing a life cycle assessment. A comparative assessment was conducted between the fossil-based process and a novel bioethanol and green ammonia approach. The ReCiPe Midpoint method was applied, utilizing Ecoinvent database in SIMAPRO. Dates to evaluate environmental impacts of adding bioethanol were obtained by using a pilot-scale reactor operating parallel to the main reactor in a Brazilian industrial unit. The scenario using bioethanol, propene, and petrochemical ammonia exhibited a noteworthy compensation for 96 kg of CO2-equiv/t of ACN, when compared to scenario 1. Additionally, this scenario achieved a 14% reduction in fossil resource scarcity. The use of bioethanol and green ammonia can reduce environmental impacts by up to 5% in the six assessed categories. Specifically, while global warming potential and fossil resource scarcity have decreased, the introduction of bioethanol has increased human toxicity and ecotoxicity impacts in ACN production, primarily due to sugar cane cultivation. The study demonstrates that the proposed innovations offer a viable approach to mitigating the environmental effects of ACN production and maintaining process safety, also highlighting the increased impacts associated with bioethanol.
{"title":"Evaluation of the Technical and Environmental Viability of a Bioethanol, Propene, and Green Ammonia Process for Acetonitrile Production through a Comprehensive Life Cycle Assessment","authors":"Izabela Silva Freitas, Aryane Maria de Oliveira Lima, Edson de Paiva Alves, Genes de Morais Souza, Luiz Antônio Magalhães Pontes","doi":"10.1021/acssuschemeng.4c09745","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09745","url":null,"abstract":"Acetonitrile (ACN) is a valuable product, serving as a feedstock in the petrochemical, pharmaceutical, and fine chemical industries. This study analyzes the environmental footprint of ACN production employing a life cycle assessment. A comparative assessment was conducted between the fossil-based process and a novel bioethanol and green ammonia approach. The ReCiPe Midpoint method was applied, utilizing Ecoinvent database in SIMAPRO. Dates to evaluate environmental impacts of adding bioethanol were obtained by using a pilot-scale reactor operating parallel to the main reactor in a Brazilian industrial unit. The scenario using bioethanol, propene, and petrochemical ammonia exhibited a noteworthy compensation for 96 kg of CO<sub>2</sub>-equiv/t of ACN, when compared to scenario 1. Additionally, this scenario achieved a 14% reduction in fossil resource scarcity. The use of bioethanol and green ammonia can reduce environmental impacts by up to 5% in the six assessed categories. Specifically, while global warming potential and fossil resource scarcity have decreased, the introduction of bioethanol has increased human toxicity and ecotoxicity impacts in ACN production, primarily due to sugar cane cultivation. The study demonstrates that the proposed innovations offer a viable approach to mitigating the environmental effects of ACN production and maintaining process safety, also highlighting the increased impacts associated with bioethanol.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143724003","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 : 2025-03-28DOI: 10.1021/acssuschemeng.4c10236
Aneela Hayder, Saikat Kumar Kuila, Shahin Mazhkoo, Rafael M. Santos, Animesh Dutta
The excessive emissions of CO2 into the atmosphere have a severe impact on the ecological environment. Activated carbon (AC) offers a promising strategy for cost-effective carbon dioxide (CO2) emissions mitigation as a solid adsorbent. The chemical activation process, which involves direct mixing of an activating agent with biomass, is a common method to achieve a porous morphology and high surface area in AC. Herein, an advanced and highly microporous activated biocarbon was synthesized using a two-step carbonization process consisting of hydrothermal synthesis of the ZnO/C carbon precursor based on condensed corn distiller soluble (CDS) followed by potassium hydroxide (KOH) activation at 700 °C for 60 min. The results indicated that the synergistic use of ZnO and K plays a complementary role in structural development and functional enhancement. This synthesis strategy resulted in advanced activated biocarbon with a significantly higher surface area of 1744.6 m2 g–1, outperforming biocarbon activated with KOH alone. In this study, it was hypothesized that KOH would penetrate and activate the ZnO/C carbon precursor more effectively than the direct activation of CDS. The resulting advanced activated biocarbon materials were systematically investigated through comprehensive microstructural, physicochemical, interfacial, textural, and thermal analyses. Scanning electron microscopy (SEM) revealed a superior 3D hierarchical structure enriched with micropores, favorable mesopores, and interconnected macropores of synthesized biocarbon. Furthermore, CO2 adsorption capacities were performed at various temperatures (273, 288, 298, and 308 K). The highest adsorption capacities, ranging from 3.70 to 6.30 mol kg–1, were observed at 1 bar and 273 K for all advanced activated biocarbon samples. Notably, the combined catalytic and templating effects of ZnO and K resulted in a highly porous structure with a high surface area, abundant adsorption sites, and excellent selective CO2 capture properties.
{"title":"Development of Advanced Activated Biocarbon from Corn Distiller Soluble via Two-Step Carbonization: Investigating the Synergistic Effects of ZnO and K toward Enhanced CO2 Capture","authors":"Aneela Hayder, Saikat Kumar Kuila, Shahin Mazhkoo, Rafael M. Santos, Animesh Dutta","doi":"10.1021/acssuschemeng.4c10236","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c10236","url":null,"abstract":"The excessive emissions of CO<sub>2</sub> into the atmosphere have a severe impact on the ecological environment. Activated carbon (AC) offers a promising strategy for cost-effective carbon dioxide (CO<sub>2</sub>) emissions mitigation as a solid adsorbent. The chemical activation process, which involves direct mixing of an activating agent with biomass, is a common method to achieve a porous morphology and high surface area in AC. Herein, an advanced and highly microporous activated biocarbon was synthesized using a two-step carbonization process consisting of hydrothermal synthesis of the ZnO/C carbon precursor based on condensed corn distiller soluble (CDS) followed by potassium hydroxide (KOH) activation at 700 °C for 60 min. The results indicated that the synergistic use of ZnO and K plays a complementary role in structural development and functional enhancement. This synthesis strategy resulted in advanced activated biocarbon with a significantly higher surface area of 1744.6 m<sup>2</sup> g<sup>–1</sup>, outperforming biocarbon activated with KOH alone. In this study, it was hypothesized that KOH would penetrate and activate the ZnO/C carbon precursor more effectively than the direct activation of CDS. The resulting advanced activated biocarbon materials were systematically investigated through comprehensive microstructural, physicochemical, interfacial, textural, and thermal analyses. Scanning electron microscopy (SEM) revealed a superior 3D hierarchical structure enriched with micropores, favorable mesopores, and interconnected macropores of synthesized biocarbon. Furthermore, CO<sub>2</sub> adsorption capacities were performed at various temperatures (273, 288, 298, and 308 K). The highest adsorption capacities, ranging from 3.70 to 6.30 mol kg<sup>–1</sup>, were observed at 1 bar and 273 K for all advanced activated biocarbon samples. Notably, the combined catalytic and templating effects of ZnO and K resulted in a highly porous structure with a high surface area, abundant adsorption sites, and excellent selective CO<sub>2</sub> capture properties.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"188 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734117","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 : 2025-03-28DOI: 10.1021/acssuschemeng.4c10844
Yao Tan, Wenhao Ni, Jianwen Yang, Yanwei Li, Zhengwei Xie, Bin Huang
The Na4Fe3(PO4)2(P2O7) (NFPP) cathode material for sodium-ion batteries (SIBs) is modified through a facile yttrium (Y)-doping approach. The crystal structures, surface morphologies, and electrochemical performances of the pristine and Y-doped samples are comparatively investigated. The results indicate that the structure and morphology of the material are almost unchanged after Y doping. Doping with an appropriate amount of Y can enhance the electronic conductivity and electrochemical kinetics of the material, leading to superior electrochemical performance. Among the four samples prepared with different Y-doping levels, the optimum one exhibits the highest capacity of 115.8 mAh g–1 (0.1C, 2–4 V, 1C = 129 mA g–1), as well as outstanding cycling stability and rate capability (retaining a capacity of 87.8 mAh g–1 after 3000 cycles at 20C, with a retention of 92.7%). Furthermore, scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements after cycling reveal that Y doping can stabilize the material structure, thereby further enhancing its lifespan during long-term cycling.
{"title":"Y-Doped Na4Fe3(PO4)2(P2O7) as a High-Performance Cathode Material for Sodium-Ion Batteries","authors":"Yao Tan, Wenhao Ni, Jianwen Yang, Yanwei Li, Zhengwei Xie, Bin Huang","doi":"10.1021/acssuschemeng.4c10844","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c10844","url":null,"abstract":"The Na<sub>4</sub>Fe<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>(P<sub>2</sub>O<sub>7</sub>) (NFPP) cathode material for sodium-ion batteries (SIBs) is modified through a facile yttrium (Y)-doping approach. The crystal structures, surface morphologies, and electrochemical performances of the pristine and Y-doped samples are comparatively investigated. The results indicate that the structure and morphology of the material are almost unchanged after Y doping. Doping with an appropriate amount of Y can enhance the electronic conductivity and electrochemical kinetics of the material, leading to superior electrochemical performance. Among the four samples prepared with different Y-doping levels, the optimum one exhibits the highest capacity of 115.8 mAh g<sup>–1</sup> (0.1C, 2–4 V, 1C = 129 mA g<sup>–1</sup>), as well as outstanding cycling stability and rate capability (retaining a capacity of 87.8 mAh g<sup>–1</sup> after 3000 cycles at 20C, with a retention of 92.7%). Furthermore, scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements after cycling reveal that Y doping can stabilize the material structure, thereby further enhancing its lifespan during long-term cycling.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"56 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734118","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 : 2025-03-27DOI: 10.1021/acssuschemeng.4c09195
Suwiwat Sangon, Nontipa Supanchaiyamat, James Sherwood, Duncan J. Macquarrie, Andrew J. Hunt
A new hindered ether solvent, namely, 2,2,6,6-tetramethyloxane, has been successfully synthesized in excellent yields (90% from 2,6-dimethyl-2,6-heptanediol and 80% from 2,6-dimethyl-5-hepten-2-ol). The physical and solvation properties of 2,2,6,6-tetramethyloxane were evaluated, which indicated its potential to replace hydrocarbon solvents and also that it imparts strong hydrogen-bond-accepting ability. VEGA models (SARpy, KNN, ISS, and CAESAR), the lazy structure–activity relationship model (Salmonella typhimurium), and the Toxicity Estimation Software Tool indicated this solvent to be nonmutagenic. The application of 2,2,6,6-tetramethyloxane in model organic reactions including the Biginelli reaction, glucose conversion to 5-hydroxymethylfurfural, and the Sonogashira reaction, importantly, validates the nonpolar nature of this solvent and exhibits its potential as an alternative solvent to hazardous hydrocarbon solvents (including toluene).
{"title":"2,2,6,6-Tetramethyloxane as an Alternative Hindered Ether Solvent for Organic Synthesis","authors":"Suwiwat Sangon, Nontipa Supanchaiyamat, James Sherwood, Duncan J. Macquarrie, Andrew J. Hunt","doi":"10.1021/acssuschemeng.4c09195","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09195","url":null,"abstract":"A new hindered ether solvent, namely, 2,2,6,6-tetramethyloxane, has been successfully synthesized in excellent yields (90% from 2,6-dimethyl-2,6-heptanediol and 80% from 2,6-dimethyl-5-hepten-2-ol). The physical and solvation properties of 2,2,6,6-tetramethyloxane were evaluated, which indicated its potential to replace hydrocarbon solvents and also that it imparts strong hydrogen-bond-accepting ability. VEGA models (SARpy, KNN, ISS, and CAESAR), the lazy structure–activity relationship model (<i>Salmonella typhimurium</i>), and the Toxicity Estimation Software Tool indicated this solvent to be nonmutagenic. The application of 2,2,6,6-tetramethyloxane in model organic reactions including the Biginelli reaction, glucose conversion to 5-hydroxymethylfurfural, and the Sonogashira reaction, importantly, validates the nonpolar nature of this solvent and exhibits its potential as an alternative solvent to hazardous hydrocarbon solvents (including toluene).","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713652","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 : 2025-03-27DOI: 10.1021/acssuschemeng.4c09579
Preeti Kang, Matej Gabrijelčič, Andraž Krajnc, Ilja Gasan Osojnik Črnivec, Blaž Likozar, Rakesh K Sharma
The conversion of lignocellulosic biomass to 5-hydroxymethylfurfural (HMF), a key renewable molecule and a potential alternative to petroleum-based chemicals, is of great research interest. In this study, we prepared a t-SiO2@B@A catalyst consisting of a mesoporous silica support, where surface −OH groups were grafted with 3-(aminopropyl)triethoxysilane (APTES), followed by functionalization with 4-formylbenzoic acid. The synthesized t-SiO2@B@A catalyst, bearing Brønsted basic (─C═N─) and acidic (−COOH) sites, exhibited bifunctional activity for the selective production of HMF from glucose in water. The structural and chemical properties of the t-SiO2@B@A catalyst were determined using various characterization techniques, such as XRD, BET, FESEM, TGA, FTIR, TPD-NH3/CO2, and solid-state cross-polarization magic angle spinning nuclear magnetic resonance (CP MAS NMR) spectroscopy, which confirmed the successful incorporation of organic moieties onto the silica support. The mesoporosity of the silica support was well maintained after surface modification, exhibiting a surface area of 266.4 m2/g, with a total acidity of 2.27 mmol/g and thermal stability up to 400 °C. The reaction system was optimized with various parameters, such as temperature, reaction time, catalyst amount, and solvents. Consequently, an HMF yield of 69.7% was achieved after 6 h at 120 °C over the t-SiO2@B@A (0.5 w/v %) catalyst. Moreover, the catalyst showed good recyclability for eight test cycles without significant loss of catalytic activity. A kinetic model was developed to monitor the conversion of glucose and the temperature dependence of HMF production. Based on numerical modeling, the first step, isomerization of glucose to fructose, was found to be slower (rate constant: kB1 = 0.348 min–1) while the second step, dehydration of fructose to HMF is faster (rate constant: kB1 = 0.348 min–1). This study provides an efficient and environmentally benign method for the conversion of glucose to HMF, highlighting its potential for industrial applications.
{"title":"Organically Functionalized Mesoporous Silica Network for One-Pot Synthesis of 5-Hydroxymethylfurfural from Glucose in Water","authors":"Preeti Kang, Matej Gabrijelčič, Andraž Krajnc, Ilja Gasan Osojnik Črnivec, Blaž Likozar, Rakesh K Sharma","doi":"10.1021/acssuschemeng.4c09579","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09579","url":null,"abstract":"The conversion of lignocellulosic biomass to 5-hydroxymethylfurfural (HMF), a key renewable molecule and a potential alternative to petroleum-based chemicals, is of great research interest. In this study, we prepared a t-SiO<sub>2</sub>@B@A catalyst consisting of a mesoporous silica support, where surface −OH groups were grafted with 3-(aminopropyl)triethoxysilane (APTES), followed by functionalization with 4-formylbenzoic acid. The synthesized t-SiO<sub>2</sub>@B@A catalyst, bearing Brønsted basic (─C═N─) and acidic (−COOH) sites, exhibited bifunctional activity for the selective production of HMF from glucose in water. The structural and chemical properties of the t-SiO<sub>2</sub>@B@A catalyst were determined using various characterization techniques, such as XRD, BET, FESEM, TGA, FTIR, TPD-NH<sub>3</sub>/CO<sub>2</sub>, and solid-state cross-polarization magic angle spinning nuclear magnetic resonance (CP MAS NMR) spectroscopy, which confirmed the successful incorporation of organic moieties onto the silica support. The mesoporosity of the silica support was well maintained after surface modification, exhibiting a surface area of 266.4 m<sup>2</sup>/g, with a total acidity of 2.27 mmol/g and thermal stability up to 400 °C. The reaction system was optimized with various parameters, such as temperature, reaction time, catalyst amount, and solvents. Consequently, an HMF yield of 69.7% was achieved after 6 h at 120 °C over the t-SiO<sub>2</sub>@B@A (0.5 w/v %) catalyst. Moreover, the catalyst showed good recyclability for eight test cycles without significant loss of catalytic activity. A kinetic model was developed to monitor the conversion of glucose and the temperature dependence of HMF production. Based on numerical modeling, the first step, isomerization of glucose to fructose, was found to be slower (rate constant: <i>k</i><sub>B1</sub> = 0.348 min<sup>–1</sup>) while the second step, dehydration of fructose to HMF is faster (rate constant: <i>k</i><sub>B1</sub> = 0.348 min<sup>–1</sup>). This study provides an efficient and environmentally benign method for the conversion of glucose to HMF, highlighting its potential for industrial applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"183 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723598","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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