This study explores the transformative role of artificial intelligence (AI) and machine learning (ML) in materials science, leveraging large language models (LLMs) such as OpenAI’s ChatGPT. Focusing on (oxy)hydroxides as oxygen evolution reaction (OER) catalysts, we demonstrate how LLMs streamline data extraction, significantly reducing reliance on traditional, time-intensive methods. Using few-shot training and strategic prompting, ChatGPT achieved an extraction accuracy of approximately 0.9. The curated data set was then used to predict OER performance via the PyCaret library to evaluate various ML algorithms and a high-accuracy XGBoost regression model with accuracies above 0.9 is subsequently established. Further analysis using SHAP and Python Symbolic Regression (PySR) identified key descriptors-electrochemical double-layer capacitance, transition metal composition, support material, and d-electron count-as critical factors, consistent with established electrochemical principles. Additionally, SHAP’s extreme values for Cu and Zn suggest unconventional catalytic roles, potentially linked to Cu2O-facilitated NiOOH formation and Zn-induced electronic modulation, demonstrating the power of data-driven analysis in uncovering hidden mechanisms. To enhance literature-based insights, Microsoft’s GraphRAG technology was employed for in-depth chemical information retrieval. Overall, this study introduces an innovative, end-to-end ML framework powered by ChatGPT, promoting broader AI adoption in scientific research and bridging computational intelligence with experimental sciences.
{"title":"Large Language Models Assisted Materials Development: Case of Predictive Analytics for Oxygen Evolution Reaction Catalysts of (Oxy)hydroxides","authors":"Chenyang Wei, Yutong Shi, Wenbo Mu, Hongyuan Zhang, Rui Qin, Yijun Yin, Gangqiang Yu, Tiancheng Mu","doi":"10.1021/acssuschemeng.5c00798","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00798","url":null,"abstract":"This study explores the transformative role of artificial intelligence (AI) and machine learning (ML) in materials science, leveraging large language models (LLMs) such as OpenAI’s ChatGPT. Focusing on (oxy)hydroxides as oxygen evolution reaction (OER) catalysts, we demonstrate how LLMs streamline data extraction, significantly reducing reliance on traditional, time-intensive methods. Using few-shot training and strategic prompting, ChatGPT achieved an extraction accuracy of approximately 0.9. The curated data set was then used to predict OER performance via the PyCaret library to evaluate various ML algorithms and a high-accuracy XGBoost regression model with accuracies above 0.9 is subsequently established. Further analysis using SHAP and Python Symbolic Regression (PySR) identified key descriptors-electrochemical double-layer capacitance, transition metal composition, support material, and d-electron count-as critical factors, consistent with established electrochemical principles. Additionally, SHAP’s extreme values for Cu and Zn suggest unconventional catalytic roles, potentially linked to Cu<sub>2</sub>O-facilitated NiOOH formation and Zn-induced electronic modulation, demonstrating the power of data-driven analysis in uncovering hidden mechanisms. To enhance literature-based insights, Microsoft’s GraphRAG technology was employed for in-depth chemical information retrieval. Overall, this study introduces an innovative, end-to-end ML framework powered by ChatGPT, promoting broader AI adoption in scientific research and bridging computational intelligence with experimental sciences.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"80 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775782","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}
The catalytic upgrading of light bio-oil (LB) is essential for enhancing the overall utilization of crude bio-oil. This study presents the synthesis of a biochar-loaded Fe catalyst (Fen-STC) via a simple one-step pyrolysis method and evaluates its performance in the upgrading of LB. The Fe species were primarily loaded onto the biochar carrier in the form of iron oxides (Fe3O4/Fe2O3), which further etched the biochar carrier, resulting in a substantial alteration of its structure and aromaticity. The optimized Fe1.0-STC exhibited a substantial increase in the specific surface area and a uniform distribution of iron oxides. Notably, this catalyst significantly enhanced the selectivity for producing five-membered ring compounds, such as cyclic ketones and furans, achieving a relative abundance of 70.23%, an increase of 87.74% compared to the control group. Further examination of hydroxyacetone and 1-hydroxy-2-butanone as model compounds elucidated the mechanisms underpinning catalytic upgrading, revealing a synergistic effect that facilitated the transformation of linear short-chain ketones into high-value cyclic compounds through aldol condensation, dehydration, and cyclization reactions. These findings suggest that the Fen-STC catalyst is a promising candidate for enhancing the quality of LB.
{"title":"Enhanced Production of Five-Membered Ring Compounds Using a Biochar-Loaded Fe Catalyst: Catalytic Upgrading of Light Bio-Oil","authors":"Shihao Lv, Hao Xu, Weiwei Wu, Yun Yu, Jie Yang, Anjiang Gao, Yong Huang, Mudassir Hussain Tahir, Kuan Ding, Shu Zhang","doi":"10.1021/acssuschemeng.5c01547","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c01547","url":null,"abstract":"The catalytic upgrading of light bio-oil (LB) is essential for enhancing the overall utilization of crude bio-oil. This study presents the synthesis of a biochar-loaded Fe catalyst (Fe<sub><i>n</i></sub>-STC) via a simple one-step pyrolysis method and evaluates its performance in the upgrading of LB. The Fe species were primarily loaded onto the biochar carrier in the form of iron oxides (Fe<sub>3</sub>O<sub>4</sub>/Fe<sub>2</sub>O<sub>3</sub>), which further etched the biochar carrier, resulting in a substantial alteration of its structure and aromaticity. The optimized Fe<sub>1.0</sub>-STC exhibited a substantial increase in the specific surface area and a uniform distribution of iron oxides. Notably, this catalyst significantly enhanced the selectivity for producing five-membered ring compounds, such as cyclic ketones and furans, achieving a relative abundance of 70.23%, an increase of 87.74% compared to the control group. Further examination of hydroxyacetone and 1-hydroxy-2-butanone as model compounds elucidated the mechanisms underpinning catalytic upgrading, revealing a synergistic effect that facilitated the transformation of linear short-chain ketones into high-value cyclic compounds through aldol condensation, dehydration, and cyclization reactions. These findings suggest that the Fe<sub><i>n</i></sub>-STC catalyst is a promising candidate for enhancing the quality of LB.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"89 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775783","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}
The separation of thorium from uranium and rare earths is of great significance for a thorium molten salt reactor nuclear energy system. Herein, a novel Aliquat 336@SiO2–P extraction resin, prepared by the in situ encapsulation of an amine-based ionic liquid (Aliquat 336) into a porous silica–polymer matrix at the same time as the polymerization, was developed for the highly selective separation of Th(IV) over U(VI) and rare earth ions. Batch adsorption studies showed that the prepared Aliquat 336@SiO2–P extraction resin has excellent selectivity, strong adsorption affinity, and high adsorption capacity for Th(IV). The adsorption process of Th(IV) follows pseudo-second-order kinetics and the Langmuir model, and the adsorption of Th(IV) is a monolayer-type, chemical, exothermic, and spontaneous process with increased entropy, achieving a maximum Th(IV) adsorption capacity (qmax) of 52.4 mg/g. Thorium is adsorbed as a complex anion in an HNO3 solution, and its adsorption conforms to the anion exchange mechanism. Furthermore, column experiments indicated that Th(IV) can be selectively separated from simulated monazite HNO3 leach liquor with a recovery rate as high as 97.7%, and the prepared extraction resin has good reusability. Compared to the conventional impregnation method, the Aliquat 336 extractant encapsulated in a porous silica–polymer matrix has significantly lower loss during the adsorption process. Overall, this new extraction resin demonstrates great application potential for the highly efficient separation and recovery of Th(IV) from monazite HNO3 leach liquor.
{"title":"Highly Selective Separation of Thorium Using an Extraction Resin by Encapsulating an Amine-Based Ionic Liquid In Situ within a Porous Silica–Polymer Matrix Instead of Conventional Impregnation Method","authors":"Zhuang Wang, Dongping Su, Ting Luo, Qiao Yu, Yiting Wang, Xingyue Liu, Xuanhao Huang, Songdong Ding","doi":"10.1021/acssuschemeng.5c00056","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00056","url":null,"abstract":"The separation of thorium from uranium and rare earths is of great significance for a thorium molten salt reactor nuclear energy system. Herein, a novel Aliquat 336@SiO<sub>2</sub>–P extraction resin, prepared by the in situ encapsulation of an amine-based ionic liquid (Aliquat 336) into a porous silica–polymer matrix at the same time as the polymerization, was developed for the highly selective separation of Th(IV) over U(VI) and rare earth ions. Batch adsorption studies showed that the prepared Aliquat 336@SiO<sub>2</sub>–P extraction resin has excellent selectivity, strong adsorption affinity, and high adsorption capacity for Th(IV). The adsorption process of Th(IV) follows pseudo-second-order kinetics and the Langmuir model, and the adsorption of Th(IV) is a monolayer-type, chemical, exothermic, and spontaneous process with increased entropy, achieving a maximum Th(IV) adsorption capacity (<i>q</i><sub>max</sub>) of 52.4 mg/g. Thorium is adsorbed as a complex anion in an HNO<sub>3</sub> solution, and its adsorption conforms to the anion exchange mechanism. Furthermore, column experiments indicated that Th(IV) can be selectively separated from simulated monazite HNO<sub>3</sub> leach liquor with a recovery rate as high as 97.7%, and the prepared extraction resin has good reusability. Compared to the conventional impregnation method, the Aliquat 336 extractant encapsulated in a porous silica–polymer matrix has significantly lower loss during the adsorption process. Overall, this new extraction resin demonstrates great application potential for the highly efficient separation and recovery of Th(IV) from monazite HNO<sub>3</sub> leach liquor.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"107 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766481","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}
Crystal phase engineering provides a promising strategy for enhancing photocatalytic hydrogen evolution performance, yet the precise impact of phase structure on activity requires further exploration. In this study, hcp- and fcc-phase Ru nanoparticles were synthesized via precursor and solvent-controlled reduction processes and integrated with TiO2. Photocatalytic hydrogen evolution tests reveal that hcp-Ru/TiO2 achieves the highest H2 production rate of 23.52 μmol/h, surpassing fcc-Ru/TiO2 (11.18 μmol/h) and bare TiO2 (4.72 μmol/h). Electrochemical and photophysical analyses demonstrate that hcp-Ru/TiO2 exhibits superior charge separation and transfer efficiency, as evidenced by the lowest charge transfer resistance, highest photocurrent response, and prolonged fluorescence lifetime. Theoretical calculations further confirm that hcp-Ru offers optimal hydrogen adsorption energy (ΔGH* = −0.14 eV), contributing to reduced overpotential and enhanced catalytic activity. This work underscores the critical role of Ru crystal phases in driving photocatalytic performance and provides new insights into phase engineering for sustainable energy applications.
{"title":"Phase-Dependent Synthesis of Ru Grown on TiO2 for Solar Driven H2 Evolution","authors":"Xiangyang Cao, Xiaohu Sun, Ganghua Zhou, Yuqi Gao, Yubo Zhou, Xiaozhi Wang, Jianjian Yi","doi":"10.1021/acssuschemeng.5c00412","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00412","url":null,"abstract":"Crystal phase engineering provides a promising strategy for enhancing photocatalytic hydrogen evolution performance, yet the precise impact of phase structure on activity requires further exploration. In this study, hcp- and fcc-phase Ru nanoparticles were synthesized via precursor and solvent-controlled reduction processes and integrated with TiO<sub>2</sub>. Photocatalytic hydrogen evolution tests reveal that hcp-Ru/TiO<sub>2</sub> achieves the highest H<sub>2</sub> production rate of 23.52 μmol/h, surpassing fcc-Ru/TiO<sub>2</sub> (11.18 μmol/h) and bare TiO<sub>2</sub> (4.72 μmol/h). Electrochemical and photophysical analyses demonstrate that hcp-Ru/TiO<sub>2</sub> exhibits superior charge separation and transfer efficiency, as evidenced by the lowest charge transfer resistance, highest photocurrent response, and prolonged fluorescence lifetime. Theoretical calculations further confirm that hcp-Ru offers optimal hydrogen adsorption energy (Δ<i>G</i><sub>H*</sub> = −0.14 eV), contributing to reduced overpotential and enhanced catalytic activity. This work underscores the critical role of Ru crystal phases in driving photocatalytic performance and provides new insights into phase engineering for sustainable energy applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"24 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775786","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 : 2025-04-03DOI: 10.1021/acssuschemeng.5c00842
Anna-Caroline Lavergne-Bril, David Peralta, Pascale Maldivi, Jean-François Colin
Imidazolate linkers selectively precipitate in pure cobalt-based hybrid materials [zeolitic-imidazolate-frameworks (ZIFs)] when they are directly added in solutions containing nickel, manganese, and cobalt. The favored reactivity of imidazole against cobalt versus other cations is deeply studied, and selectivity mechanisms are explained, thanks to experimental data supported by DFT calculations. The preferential coordination of imidazole with cobalt instead of nickel cations is explained, thanks to the tetrahedral Co(Im)4 cluster formation, which is the main building block of ZIF structures. On the other hand, the cobalt/manganese selectivity is kinetically driven. Different ligands from the imidazole family have been compared, and a direct correlation between cobalt/manganese selectivity and pKa of molecules has been highlighted.
{"title":"Highlighting the Cobalt Selective Precipitation Mechanism of Imidazole Linkers into a Multimetallic Solution (Ni, Co, and Mn)","authors":"Anna-Caroline Lavergne-Bril, David Peralta, Pascale Maldivi, Jean-François Colin","doi":"10.1021/acssuschemeng.5c00842","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00842","url":null,"abstract":"Imidazolate linkers selectively precipitate in pure cobalt-based hybrid materials [zeolitic-imidazolate-frameworks (ZIFs)] when they are directly added in solutions containing nickel, manganese, and cobalt. The favored reactivity of imidazole against cobalt versus other cations is deeply studied, and selectivity mechanisms are explained, thanks to experimental data supported by DFT calculations. The preferential coordination of imidazole with cobalt instead of nickel cations is explained, thanks to the tetrahedral Co(Im)<sub>4</sub> cluster formation, which is the main building block of ZIF structures. On the other hand, the cobalt/manganese selectivity is kinetically driven. Different ligands from the imidazole family have been compared, and a direct correlation between cobalt/manganese selectivity and p<i>K</i><sub>a</sub> of molecules has been highlighted.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"33 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775785","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 : 2025-04-03DOI: 10.1021/acssuschemeng.5c00541
Liang Wang, Fengshuo Xi, Jie Yu, Shaoyuan Li, Jijun Lu, Zhongqiu Tong, Xiuhua Chen, Kuixian Wei, Wenhui Ma
The trend of large-scale wafer thinning has led to increased surface activity, oxidation, and uneven oxidation interfaces in photovoltaic silicon cutting waste (SCW) produced by diamond wire cutting, posing significant challenges for its use as a silicon–carbon anode material. To address these issues, we propose a green recycling method that utilizes alkaline solutions to recover silicates from etched SCWs, avoiding the highly corrosive HF acid. By combining inexpensive chitosan (CTS) as a soft template, we achieve controllable reshaping of silicates into amorphous oxide layers (1 to 16 nm) on submicron SCW surfaces. This process involves a one-step method in a vacuum autoclave, which simultaneously eliminates the chitosan template and forms both the oxide layer and the phenolic resin. Unlike self-crystallizing oxide layers, the amorphous layers ensure uniform expansion and contraction, facilitate Li+ transfer, and introduce structural defects, enhancing lithium storage performance. The resulting Si@SiOx@C composite with a 5 nm thick oxide interface significantly improves the cycling performance, coulombic efficiency, and rate capability of the silicon–carbon material, achieving a reversible capacity of over 1000 mAh g–1 after 200 cycles at 1 A g–1. This work demonstrates the value-added utilization of submicron SCWs in the commercial production of high-performance silicon-based lithium-ion battery anodes.
{"title":"Novel, Clean, and Controlled Method for Surface Oxidation of Photovoltaic Silicon Cutting Waste for High-Performance Si–C Anode Materials","authors":"Liang Wang, Fengshuo Xi, Jie Yu, Shaoyuan Li, Jijun Lu, Zhongqiu Tong, Xiuhua Chen, Kuixian Wei, Wenhui Ma","doi":"10.1021/acssuschemeng.5c00541","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00541","url":null,"abstract":"The trend of large-scale wafer thinning has led to increased surface activity, oxidation, and uneven oxidation interfaces in photovoltaic silicon cutting waste (SCW) produced by diamond wire cutting, posing significant challenges for its use as a silicon–carbon anode material. To address these issues, we propose a green recycling method that utilizes alkaline solutions to recover silicates from etched SCWs, avoiding the highly corrosive HF acid. By combining inexpensive chitosan (CTS) as a soft template, we achieve controllable reshaping of silicates into amorphous oxide layers (1 to 16 nm) on submicron SCW surfaces. This process involves a one-step method in a vacuum autoclave, which simultaneously eliminates the chitosan template and forms both the oxide layer and the phenolic resin. Unlike self-crystallizing oxide layers, the amorphous layers ensure uniform expansion and contraction, facilitate Li<sup>+</sup> transfer, and introduce structural defects, enhancing lithium storage performance. The resulting Si@SiOx@C composite with a 5 nm thick oxide interface significantly improves the cycling performance, coulombic efficiency, and rate capability of the silicon–carbon material, achieving a reversible capacity of over 1000 mAh g<sup>–1</sup> after 200 cycles at 1 A g<sup>–1</sup>. This work demonstrates the value-added utilization of submicron SCWs in the commercial production of high-performance silicon-based lithium-ion battery anodes.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766480","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}
The scarcity of freshwater resources represents a significant challenge to the advancement of humanity and society. While solar-driven interfacial evaporation technology offers distinctive advantages, the acquisition and preparation of photothermal materials have significantly hindered its further development. Herein, we introduce a novel approach employing porous sand disc (PSD) as a photothermal material, showcasing exceptional evaporation performance. The natural sand is transformed into a micron-sized superhydrophilic PSD, which is then used to design a one-dimensional and self-water-supplied T-shaped evaporator (T-PSD), that is similar in function to plant transpiration. The T-PSD demonstrates a remarkable evaporation rate of 1.428 kg/(m2·h) with low surface temperature (36.5 °C) under 1 sun, resulting in an impressive evaporation efficiency of 86.1%. The T-PSD maintains a high evaporation performance even when evaporating salt water, attributed to the PSD crystallizing preferentially at the edge. The edge-preferential crystallization significantly enhances the evaporator’s continuous operational capability. Leveraging abundant and cost-effective natural sand as a photothermal material offers a sustainable development approach for advancing interfacial evaporation technology.
{"title":"Porous Sand Disc: A Sustainable Approach for High-Efficiency Solar-Driven Evaporation","authors":"Changzheng Li, Jiaqiang Liao, Jingying Dai, Tao Rui, Hengyi Guo, Xiantao Zhang, Yanjun Chen, Zhi Qun Tian","doi":"10.1021/acssuschemeng.5c01740","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c01740","url":null,"abstract":"The scarcity of freshwater resources represents a significant challenge to the advancement of humanity and society. While solar-driven interfacial evaporation technology offers distinctive advantages, the acquisition and preparation of photothermal materials have significantly hindered its further development. Herein, we introduce a novel approach employing porous sand disc (PSD) as a photothermal material, showcasing exceptional evaporation performance. The natural sand is transformed into a micron-sized superhydrophilic PSD, which is then used to design a one-dimensional and self-water-supplied T-shaped evaporator (T-PSD), that is similar in function to plant transpiration. The T-PSD demonstrates a remarkable evaporation rate of 1.428 kg/(m<sup>2</sup>·h) with low surface temperature (36.5 °C) under 1 sun, resulting in an impressive evaporation efficiency of 86.1%. The T-PSD maintains a high evaporation performance even when evaporating salt water, attributed to the PSD crystallizing preferentially at the edge. The edge-preferential crystallization significantly enhances the evaporator’s continuous operational capability. Leveraging abundant and cost-effective natural sand as a photothermal material offers a sustainable development approach for advancing interfacial evaporation technology.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"58 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766482","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 : 2025-04-03DOI: 10.1021/acssuschemeng.5c01296
Shuangshuang Cha, Yizhou Yang, Yujia Liu, Chenyang Zhao, Yupeng Tian, Wei Xu, Wei Du, Mengxin Qu, Hanlin Jin, Xuejing Yang, Bing Sun, Ming Gong
Electrocatalytic oxidation is an emerging substitute for industrially relevant oxidation processes due to its mild conditions and high safety, and the catalytic performance is not only associated with the catalyst structure but also closely related to the interfacial ionic microenvironment. In this work, by using electrocatalytic olefin epoxidation as a representative example, we elucidated the different influencing mechanisms of the interfacial ionic environment toward two distinct mechanisms of indirect oxidation and direct oxidation through a combinatory study via kinetics, capacitance analysis, in situ spectroscopy, and theoretical calculation. In the indirect epoxidation system, the reaction pathway involves the hydrophilic activation of the mediator and its further reaction with olefin near the hydrophobic environment. The hydrophilicity/hydrophobicity characteristics of the anions tailor the interface for dispersing the solvent domains and active species, and the amphipathic sulfonimide anions create optimal performance. In the direct epoxidation system, the large olefin substrate must penetrate into the densely packed anion double layer to contact the surface oxygen species generated in situ on the electrode to be epoxidized, and the limiting factor turns into the crowdedness of the double layer or the anion size. The smaller tetrafluoroborate anions outperformed other larger anions by minimally impacting mass transfer. This work not only highlights the key role of the interfacial ionic environment in modulating organic electrosynthesis but also emphasizes the distinct influences of the microenvironment under different reaction pathways.
{"title":"Pathway-Dependent Ion Effects for Electrocatalytic Olefin Epoxidation","authors":"Shuangshuang Cha, Yizhou Yang, Yujia Liu, Chenyang Zhao, Yupeng Tian, Wei Xu, Wei Du, Mengxin Qu, Hanlin Jin, Xuejing Yang, Bing Sun, Ming Gong","doi":"10.1021/acssuschemeng.5c01296","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c01296","url":null,"abstract":"Electrocatalytic oxidation is an emerging substitute for industrially relevant oxidation processes due to its mild conditions and high safety, and the catalytic performance is not only associated with the catalyst structure but also closely related to the interfacial ionic microenvironment. In this work, by using electrocatalytic olefin epoxidation as a representative example, we elucidated the different influencing mechanisms of the interfacial ionic environment toward two distinct mechanisms of indirect oxidation and direct oxidation through a combinatory study via kinetics, capacitance analysis, in situ spectroscopy, and theoretical calculation. In the indirect epoxidation system, the reaction pathway involves the hydrophilic activation of the mediator and its further reaction with olefin near the hydrophobic environment. The hydrophilicity/hydrophobicity characteristics of the anions tailor the interface for dispersing the solvent domains and active species, and the amphipathic sulfonimide anions create optimal performance. In the direct epoxidation system, the large olefin substrate must penetrate into the densely packed anion double layer to contact the surface oxygen species generated in situ on the electrode to be epoxidized, and the limiting factor turns into the crowdedness of the double layer or the anion size. The smaller tetrafluoroborate anions outperformed other larger anions by minimally impacting mass transfer. This work not only highlights the key role of the interfacial ionic environment in modulating organic electrosynthesis but also emphasizes the distinct influences of the microenvironment under different reaction pathways.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"38 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766485","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 : 2025-04-02DOI: 10.1021/acssuschemeng.4c10624
Xiaoqing Lin, Xingyu Zan, Yuxuan Ying, Panjie Ji, Angjian Wu, Qi Lu, Qunxing Huang, Xiaodong Li, Jianhua Yan
Offshore carbon capture utilization and storage (CCUS) is essential for addressing greenhouse gas emissions in China’s emission-intensive, land-constrained coastal regions. This study combines a dynamic reservoir estimation model with a drilling economic model to develop a multiwell optimization scheme that efficiently balances cost efficiency and storage capacity. The cost of saline aquifer storage varies from $3.69 to $12.51/tCO2. A multiphase offshore storage source-sink matching model underpinned by a multiwell optimization framework is proposed to minimize full-process costs by integrating emission sources, coastal hubs, transport pipelines, and storage sinks. The network is economically optimized over a 25 year planning horizon to identify the optimal matching schemes, pipeline development, and phased economic evaluations. The results suggest that a 4.59 Gt emission reduction from 154 stationary sources in Zhejiang Province is economically feasible at an expenditure of $236.03 billion. The optimal CCUS network incurs a unit cost of $51.22/tCO2, dominated by capture cost at 84.23%. The Qiantang, Minjiang, and Fuzhou basins are progressively developed and utilized. Notably, as the learning rate of technological advancements increases from 0.02 to 0.08, the unit capture cost decreases by 50.12%. This study provides guidance for the green low-carbon transition of offshore storage in the coastal regions of China.
{"title":"Technoeconomic Assessment of Offshore Carbon Storage Multiphase Source-Sink Matching Based on Multiwell Optimization in Eastern Coastal China","authors":"Xiaoqing Lin, Xingyu Zan, Yuxuan Ying, Panjie Ji, Angjian Wu, Qi Lu, Qunxing Huang, Xiaodong Li, Jianhua Yan","doi":"10.1021/acssuschemeng.4c10624","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c10624","url":null,"abstract":"Offshore carbon capture utilization and storage (CCUS) is essential for addressing greenhouse gas emissions in China’s emission-intensive, land-constrained coastal regions. This study combines a dynamic reservoir estimation model with a drilling economic model to develop a multiwell optimization scheme that efficiently balances cost efficiency and storage capacity. The cost of saline aquifer storage varies from $3.69 to $12.51/t<sub>CO2</sub>. A multiphase offshore storage source-sink matching model underpinned by a multiwell optimization framework is proposed to minimize full-process costs by integrating emission sources, coastal hubs, transport pipelines, and storage sinks. The network is economically optimized over a 25 year planning horizon to identify the optimal matching schemes, pipeline development, and phased economic evaluations. The results suggest that a 4.59 Gt emission reduction from 154 stationary sources in Zhejiang Province is economically feasible at an expenditure of $236.03 billion. The optimal CCUS network incurs a unit cost of $51.22/t<sub>CO2</sub>, dominated by capture cost at 84.23%. The Qiantang, Minjiang, and Fuzhou basins are progressively developed and utilized. Notably, as the learning rate of technological advancements increases from 0.02 to 0.08, the unit capture cost decreases by 50.12%. This study provides guidance for the green low-carbon transition of offshore storage in the coastal regions of China.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"38 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766538","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 : 2025-04-02DOI: 10.1021/acssuschemeng.4c10583
Qu Yue, Yu Wan, Lu Qiu, Junhui He, Yuhang Chen, Taotao Gao, Qian Zhao, Xiaoqin Li, Dan Xiao
An economical and eco-friendly food sweetener erythritol with abundant hydroxyl groups and suitable site resistance has been added to ZnSO4 electrolytes in aqueous Zn ion batteries (AZIBs). Density functional theory (DFT) calculations demonstrate that the O atoms in erythritol molecules can supply electrons to Zn2+, thus mitigating an electron transfer from H2O to Zn2+, resulting in erythritol entering the solvation structure of Zn[(H2O)6]2+ and replacing some water molecules. Spectroscopic analysis confirms the altered solvation structure of Zn2+ and the reconstructed hydrogen-bonding network of the ZnSO4 and erythritol electrolytes. With an equilibrium between “network water” and “free water” induced by erythritol additives, the possibility of active water decomposition is degraded, which further inhibits water-splitting and corrosion side reactions. In addition, theoretical studies and experimental characterizations verify that erythritol additives preferentially adsorb on the surface of Zn anodes, thus effectively protecting Zn anodes and inhibiting the mad growth of dendrites. As a result, the cells with ZnSO4 + erythritol electrolytes demonstrated significantly higher Coulombic efficiency values and longer lifetimes than those of pure ZnSO4 electrolytes. This study could advance the research process of small-molecule polyol additives for AZIBs.
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